bluuebunny/crossref_metadata_2025 huggingface dataset:
Conformational Studies on Oligosubstituted Adamantane Derivatives – Structural Features of Tetravinyl‐, Tetracyclopropyl‐, and Tetraisopropyladamantane
Authors: Kozhushkov Sergei I. , Yufit Dmitry S. , Boese Roland , Bläser Dieter , Schreiner Peter R. , de Meijere Armin
Published: April 2005

1,3‐Diisopropyl‐ (4), 1‐tert‐butyl‐3‐isopropyl‐ (5), 1,3,5‐triisopropyl‐ (6) and 1‐tert‐butyl‐3,5‐diisopropyladamantane (7) were prepared from the same synthetic precursor – methyl 3‐isopropyladamantane‐1‐carboxylate (10) – applying a standard set of repetitive procedures in 65, 77, 24, and 34 % overall yield, respectively. 1,3,5,7‐Tetraethenyladamantane (17) was obtained in two steps – Swern oxidation and Wittig olefination – from 1,3,5,7‐tetrakis(hydroxymethyl)adamantane (15) in 45 % overall yield and converted into 1,3,5,7‐tetracyclopropyladamantane (8) by fourfold cyclopropanation with diazomethane catalyzed by palladium(II) acetate (91 % yield). Hydrogenolysis of 8 over a platinum catalyst furnished 1,3,5,7‐tetraisopropyladamantane (9) in quantitative yield. 1‐Isopropyladamantane (3) as well as the hydrocarbons 4–7 did not give any crystals suitable for X‐ray crystal structure analysis, even when using the Optical Heating and Crystallization Device (OHCD). This method was rather successful when applied to the tetravinyl derivative 17, X‐ray crystal structure analysis of which revealed an approximately C2‐symmetric conformation in the solid state at 150 K. However, no well‐defined orientation was detected for the cyclopropyl groups in 8, and the molecules were severely disordered even at 30(1) K. In contrast to this, X‐ray crystal structure analysis of the tetraisopropyl derivative 9 revealed an S4‐symmetric conformation for this hydrocarbon at 203 K. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Heck Reaction of Protected Allyl Alcohols with Aryl Bromides Catalyzed by a Tetraphosphanepalladium Complex
Authors: Berthiol Florian , Doucet Henri , Santelli Maurice
Published: April 2005

A range of aryl bromides undergo a Heck vinylation reaction with a protected allyl alcohol in the presence of[PdCl(C3H5)]2/cis,cis,cis‐1,2,3,4‐tetrakis(diphenylphosphan‐ylmethyl)cyclopentane as a catalyst. The reactivity of these allyl alcohol derivatives using a variety of protecting groups has been studied. The best results in terms of substrate/catalyst ratio were obtained with a THP protecting group. In most cases, the major isomer obtained was the (E)‐cinnamyl alcohol derivative. The reaction tolerates several functionalities, such as trifluoromethyl, methoxy, dimethylamino, acetyl, formyl or nitrile. Furthermore, this catalyst can be used at low loadings, even for reactions with sterically hindered substrates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Synthesis and Absolute Configuration of Hyperaspine, an Alkaloid of the Ladybird Hyperaspis campestris
Authors: Dooms Cédric , Laurent Pascal , Daloze Désiré , Pasteels Jacques , Nedved Oldrich , Braekman Jean‐Claude
Published: April 2005

Hyperaspine (1a), isolated from the European Coccinellidae Hyperaspis campestris, isthe first representative of a new type of ladybird alkaloids having a 3‐oxaquinolizidine skeleton. A new total synthesis of (±)‐hyperaspine starting from protected piperidin‐4‐one has been achieved. The absolute configuration of the natural alkaloid was unequivocally established to be 3S,4aS,6R,8S by HPLC analyses on a chiral column. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
A Pauson–Khand Approach to New Carbocyclic Nucleoside Analogs
Authors: Lanver Andreas , Schmalz Hans‐Günther
Published: April 2005

The synthesis of three new carbocyclic nucleoside analogs (CNAs) with the nucleobase attached to a 3′‐hydroxymethylcyclopent‐2′‐en‐1′‐yl scaffold is reported. A variety of symmetric dienynes (propargylic acetals of type 11) were used as substrates in a cobalt‐mediated Pauson–Khand (PK) reaction to give bicyclic cyclopentenone derivatives of type rac‐12 with high diastereoselectivity. These compounds are valuable building blocks for the synthesis of structurally diverse CNAs with a high biological potential as apoptosis‐inducing agents. Starting from the PK product rac‐12a, the synthesis of 4′‐trialkylsilyloxyethyl‐substituted nucleosides rac‐18 and rac‐19 (with 5‐bromouracil and 6‐chloropurine as a nucleo‐base, respectively) was accomplished in seven steps (28 % and 37 % overall yield). The regio‐ and diastereoselective nucleobase (NB) introduction was achieved by Pd0‐catalyzed allylic substitution. Starting from the PK product rac‐12e, the 2′‐phenyl‐4′‐trialkylsilyloxymethyl‐substituted CNA rac‐17 was prepared (6 steps, 29 % yield)by exploitingan alternative protocol — a Mitsunobu reaction — for the NB introduction. The key intermediates 12a and 12e were obtained in virtually enantiopure form by kinetic resolution by means of oxazaborolidine‐catalyzed borane reduction (CBS reduction) in the presence of a (R)‐diphenylprolinol‐derived B‐methyl oxazaborolidine catalyst. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
The RuO4‐Catalyzed Ketohydroxylation, Part II:A Regio‐, Chemo‐ and Stereoselectivity Study
Authors: Plietker Bernd
Published: April 2005

The direct RuO4‐catalyzed ketohydroxylation of olefins is a new and convenient method for the preparation of a wide range of symmetrical and unsymmetrical α‐hydroxy ketones. Since reactions in which two different functional groups are introduced in one step always involve regio‐, chemo‐ and stereoselectivity issues, this paper gives a full account of investigations of various selectivity aspects in the ketohydroxylation. Stereoselectivity issues were examined in the final part of the present report. The Kishi rules, known from OsO4‐catalyzed dihydroxylations, are found to be valid for the RuO4‐catalyzed ketohydroxylation and lead to moderate to good diastereomeric ratios in the oxidation of olefins possessing an allylic center of chirality. Furthermore, competition experiments between different substituted olefins led to a reactivity profile applicable to the prediction of which is the most reactive of different C=C double bonds present in a molecule. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Earth hummocks (thúfur): new insights to their thermal characteristics and development in eastern Lesotho, southern Africa
Authors: Grab Stefan W.
Published: April 2005

The aspect‐controlled variations in soil freezing within earth hummocks of eastern Lesotho (southern Africa) are analysed. Ground thermal data were measured for an earth hummock from late autumn to early spring in 1995 and 1996, using Tinytalk™ data loggers. During 1995, ground temperatures were recorded at 15 and 20 cm depth on the hummock north, east, south and west aspects, whilst in 1996 temperatures were recorded at 1 cm, 5 cm and 10 cm on the north and south aspects. The data from 1995 indicate that soil freezing commences on the hummock southern aspects and gradually progresses towards the western and northern aspects, whilst the eastern aspect remained unfrozen throughout winter. The data from 1996 indicate that a thick snow cover almost nullifies the temperature differences between the hummock northern and southern aspects. However, given the relative absence of snow during contemporary winters, freeze intensity and duration is longest on the hummock southern and western aspects, which helps explain earth hummock deformation (elongation and coalescence) in a southwesterly direction on slope gradients ≤3°. Copyright © 2005 John Wiley & Sons, Ltd.
Testing a statistical curve‐fitting procedure for quantifying sediment populations within multi‐modal particle‐size distributions
Authors: Leys John , McTainsh Grant , Koen Terry , Mooney Brian , Strong Craig
Published: April 2005

This paper describes a series of tests designed to evaluate the capacity of a personal computer (PC) based statistical curve‐fitting program called MIX to quantify composite populations within multi‐modal particle‐size distributions. Three natural soil samples were analysed by a Coulter Multisizer, and their particle‐size distributions analysed using MIX software to identify the modes, standard deviations and proportions of their composite populations. The particle‐size distributions of the three natural soil samples were then numerically combined in equal proportions using a spreadsheet program to create synthetic particle‐size distributions of known populations. MIX was then tested on the synthetic particle‐size distributions to see if the modes and proportions it identified were similar to those modes and proportions known to characterize the synthetic particle‐size distributions. The main outcome is that MIX can very accurately describe the modal particle size and proportions of the major composite populations within a particle‐size distribution. However MIX has difficulty in identifying small populations (those contributing <10 per cent of a total particle‐size distribution), particularly when they are located in the central sections of particle‐size distributions, overlain by larger populations, or when positioned in the fine tails of distributions. Despite these minor shortcomings, MIX is a valuable tool for the examination and interpretation of particle‐size data. Copyright © 2005 John Wiley & Sons, Ltd.
Provenance of long‐travelled dust determined with ultra‐trace‐element composition: a pilot study with samples from New Zealand glaciers
Authors: Marx Samuel K. , Kamber Balz S. , McGowan Hamish A.
Published: April 2005

We report high‐precision inductively coupled plasma mass spectrometric (ICP‐MS) compositional data for 39 trace elements in a variety of dust deposits, trapped sediments and surface samples from New Zealand and Australia. Dusts collected from the surface of alpine glaciers in the Southern Alps, New Zealand, believed to have undergone long‐distance atmospheric transport from Australia, are recognizable on account of their overabundances of Pb and Cu with respect to typical upper crustal values. Long‐travelled dust from Australia therefore scavenges these and other metals (e.g. Zn, Sb and Cd) from the atmosphere during transport and deposition. Hence, due to anthropogenic pollution, long‐travelled Australian dusts can be recognized by elevated metal contents.

The relative abundance of 25 other elements that are not affected by atmospheric pollution, mineral sorting (Zr and Hf) and weathering[sol ]solubility (alkali and earth alkali elements) reflects the geochemistry of the dust source sediment. As a result, we are able to establish the provenance of dust using ultra‐trace‐element chemistry at regional scale. Comparison of long‐travelled dust chemistry with potential Australian sources shows that fits of variable quality are obtained. We propose that the best fitting potential source chemistry most likely represents the major dust source area. A binary mixing model is used to demonstrate that admixture of small quantities of local dust provides an even better fitting dust chemistry for the long‐travelled dusts. Copyright © 2005 John Wiley & Sons, Ltd.
Geomorphic imprint of landslides on alpine river systems, southwest New Zealand
Authors: Korup Oliver
Published: April 2005

An inventory of 846 mass movements, mainly landslides, in two alpine regions of southwest New Zealand was created to explore the geomorphic impacts of slope‐failure processes on river channels and valley floors. In total, 213 (i.e. 27 per cent) of the slope failures descended to valley floors, affecting the geomorphology of trunk channels (catchment area AC > 10 km2) and valley floors in recurring patterns. A nominal classification system is introduced for characterizing (a) the physical contact nature between landslides and river channels, and (b) the resulting geomorphic consequences for drainage. Although landslide area A is useful for estimating the length of channel directly impacted by debris, it does not necessarily predict the direction of fluvial response or type of impact. Dominant persistent geomorphic imprints of bedrock landslides include channel occlusions and landslide dams in South Westland and Fiordland, respectively. Differences in size distribution and geomorphic effects on river systems between the two study regions are attributed to bedrock geology, tectonics and sediment flux. Although South Westland rivers are more frequently affected by landslides, disrupting long‐term effects such as blockage are more persistent in Fiordland. Copyright © 2005 John Wiley & Sons, Ltd.
The Chemical and Structural Nature of Proton Exchange Membrane Fuel Cell Properties
Authors: Hickner M. A. , Pivovar B. S.
Published: April 2005

The chemical and structural (morphological) features of proton exchange membranes are directly tied to their fuel cell relevant transport properties. A large body of research has focused on characterizing the structure or investigating the properties of Nafion® and other proton exchange membranes, but few studies have linked chemical composition to membrane morphology, and resulting transport properties. This paper systematically discusses the key chemical and structural features of proton exchange membranes that impact properties critical for fuel cell applications. We focus our discussion on the fuel cell relevant transport properties of proton conductivity, methanol permeability, water diffusion coefficient, and electro‐osmotic drag coefficient, using evidence from our work and from the literature to illustrate the connection between structure and properties in these materials. It is hoped that this document will serve as a guide to the rational, systematic design of new proton exchange membrane materials with improved properties.
Synthesis and Characterization of Pyridine‐Based Polybenzimidazoles for High Temperature Polymer Electrolyte Membrane Fuel Cell Applications
Authors: Xiao L. , Zhang H. , Jana T. , Scanlon E. , Chen R. , Choe E.‐W. , Ramanathan L. S. , Yu S. , Benicewicz B. C.
Published: April 2005

A series of polybenzimidazoles (PBIs) incorporating main chain pyridine groups were synthesized from the pyridine dicarboxylic acids (2,4‐, 2,5‐, 2,6‐ and 3,5‐) and 3,3′,4,4′‐tetraaminobiphenyl, using polyphosphoric acid (PPA) as both solvent and polycondensation reagent. A novel process, termed the PPA process, has been developed to prepare phosphoric acid (PA) doped PBI membranes by direct‐casting of the PPA polymerization solution without isolation or re‐dissolution of the polymers. The subsequent hydrolysis of PPA to PA by moisture absorbed from the atmosphere usually induced a transition from the solution state to a gel‐like state and produced PA‐doped PBI membranes with a desirable suite of physiochemical properties. The polymer structure characterization included inherent viscosity (I.V.) determination as a measurement of polymer molecular weight and thermal stability assessment via thermogravimetric analysis. Physiochemical properties of the doped membrane were studied by measurements of the PA doping level, ionic conductivity and mechanical properties. The resulting pyridine‐based polybenzimidazole membranes displayed high PA doping levels, ranging from 15 to 25 mol of PA per PBI repeat unit, which contributed to their unprecedented high proton conductivities of 0.1 to 0.2 S cm–1 at 160 °C. The mechanical property measurements showed that the pyridine‐based PBI membranes were thermally stable and maintained mechanical integrity even at high PA doping levels. Preliminary fuel cell tests demonstrated the feasibility of the novel pyridine‐based PBI (PPBI) membranes from the PPA process for operating fuel cells at temperatures in excess of 120 °C without any external humidification.
Chemical Modification of Perfluorosulfo‐nated Membranes with Pyrrole for Fuel Cell Application: Preparation, Characteri‐sation and Methanol Transport
Authors: Xu F. , Innocent C. , Bonnet B. , Jones D. J. , Rozière J.
Published: April 2005

In situ chemical polymerisation of pyrrole in Nafion®‐115 membranes produces a composite material that shows a decrease in methanol crossover compared with the non‐modified material, and a good protonic conduction (area resistance of 0.65 Ω cm2). Pyrrole is impregnated from an appropriate solvent, and the choice of oxidising agent (hydrogen peroxide, ammonium peroxodisulfate) provides two types of modified membrane. Membrane characterisation using infrared spectroscopy shows the presence of pyrrole oligomers and polymer, but the proton conductivity is lower than that of the Nafion®‐115 membrane by only a factor 2–3. Methanol transport measurements in 2 mol dm–3 methanol with and without application of an electric field show ca. 30% lower crossover for the pyrrole‐modified membranes. In single cell hydrogen – oxygen fuel cell tests, the pyrrole‐modified Nafion® prepared using hydrogen peroxide oxidant gave higher open circuit voltage and current density, in particular at > 80 °C, than non‐modified Nafion®‐115.
Recent Developments on Proton Conduc‐ting Poly(2,5‐benzimidazole) (ABPBI) Membranes for High Temperature Poly‐mer Electrolyte Membrane Fuel Cells
Authors: Asensio J. A. , Gómez‐Romero P.
Published: April 2005

Commercial polybenzimidazole (PBI) membranes impregnated with phosphoric acid have become a serious candidate as electrolytes for high temperature PEMFC. Much research effort has been devoted to the study of this proton conducting membrane.[1, 2] On the other hand, PBI is not the simplest nor the cheapest of this family and many other polybenzimidazoles would also be of great interest in this respect. Among them, poly(2,5‐benzimidazole) (ABPBI) is one of the best choices [3]. ABPBI is easy to polymerize from a single monomer, even without previous purification, it absorbs more acid than PBI in the same bath concentration, and it has the same thermal stability and high proton conductivity at temperatures up to 200 °C. Here we review all the recent developments on the preparation of proton conducting ABPBI membranes, mainly by phosphoric acid impregnation, but also by sulfonation or doping with heteropolyacids to form hybrid organic‐inorganic membranes.
Enhanced susceptibility of S‐100B transgenic mice to neuroinflammation and neuronal dysfunction induced by intracerebroventricular infusion of human β‐amyloid
Authors: Craft Jeffrey M. , Watterson D. Martin , Marks Alexander , Van Eldik Linda J.
Published: April 2005

S‐100B is an astrocyte‐derived protein that is increased in focal areas of the brain most severely affected by neuropathological changes in Alzheimer's disease (AD). Cell‐based and clinical studies have implicated S‐100B in progression of a pathologic, glial‐mediated pro‐inflammatory state in the CNS. However, the relationship between S‐100B levels and susceptibility to AD‐relevant neuroinflammation and neuronal dysfunction in vivo has not been determined. To test the hypothesis that overexpression of S‐100B increases vulnerability to β‐amyloid (Aβ)‐induced damage, we used S‐100B‐overexpressing transgenic (Tg) and S‐100B knockout (KO) mice in a mouse model that involves intracerebroventricular infusion of human oligomeric Aβ1‐42. This model mimics many features of AD, including robust neuroinflammation, Aβ plaques, synaptic damage and neuronal loss in the hippocampus. S‐100B Tg, KO, and wild‐type (WT) mice were infused with Aβ for 28 days, sacrificed at 60 days, and hippocampal endpoints analyzed. We found that Tg mice showed increased vulnerability to Aβ‐induced neuropathology relative to either WT or KO mice. Specifically, Tg mice exhibited enhanced glial activation and neuroinflammation, increased nitrotyrosine staining (a marker of glial‐induced neuronal damage), and more pronounced loss of synaptic markers. Interestingly, Tg mice showed no significant differences in Aβ plaque burden compared with WT or KO mice, suggesting that, as in the human situation, the severity of neuronal dysfunction did not correlate with amyloid deposition. Our data are consistent with a model in which S‐100B overexpression in AD enhances glial activation and leads to an augmented neuroinflammatory process that increases the severity of neuropathologic sequelae. © 2005 Wiley‐Liss, Inc.
Trifunctional bispecific antibody–induced tumor cell lysis of squamous cell carcinomas of the upper aerodigestive tract
Authors: Gronau Silke S. , Schmitt Michael , Thess Bernard , Reinhardt Peter , Wiesneth Markus , Schmitt Anita , Riechelmann Herbert
Published: April 2005

Background.

The trifunctional bispecific antibody Removab (tbAB) bridges and activates CD3 positive T cells to EpCAM on carcinoma cells and simultaneously binds to an accessory immune‐cell inducing tumor cell lysis. tbAB‐induced tumor cytotoxicity was assessed in an autologous human ex vivo system.

Methods.

One hundred forty tumor samples and autologous peripheral blood mononuclear cells from a total of 36 patients with head and neck squamous cell carcinomas (HNSCCs) were incubated on a chicken embryo chorioallantois membrane with Removab. Tumor cells coincubated with cisplatin or cell culture medium served as positive and negative controls. Tumor cell lysis was assessed by acridine orange staining or by fluorescence‐activated cell sorting of propidium iodide–marked cells after 24 and 48 hours (T24/T48) coincubation.

Results.

Coincubation of HNSCC cells with tbAB and autologous peripheral blood mononuclear cells resulted in a 49% ± 6% decrease of viable cells at T24 (p < .005) and in a decrease of 56% ± 8% at T48 (p < .005) compared with the control. The tumor cytotoxicity was similar to that of cisplatin (49% ± 7% decrease at T24 and 49% ± 8% at T48).

Conclusion.

In an autologous human ex vivo system, the tbAB‐induced tumor cell lysis was comparable to that by cisplatin. © 2005 Wiley Periodicals, Inc. Head Neck 27: XXX–XXX, 2005
High‐throughput protein expression analysis using tissue microarray technology of a large well‐characterised series identifies biologically distinct classes of breast cancer confirming recent cDNA expression analyses
Authors: Abd El‐Rehim Dalia M. , Ball Graham , Pinder Sarah E. , Rakha Emad , Paish Claire , Robertson John F.R. , Macmillan Douglas , Blamey Roger W. , Ellis Ian O.
Published: April 2005

Recent studies on gene molecular profiling using cDNA microarray in a relatively small series of breast cancer have identified biologically distinct groups with apparent clinical and prognostic relevance. The validation of such new taxonomies should be confirmed on larger series of cases prior to acceptance in clinical practice. The development of tissue microarray (TMA) technology provides methodology for high‐throughput concomitant analyses of multiple proteins on large numbers of archival tumour samples. In our study, we have used immunohistochemistry techniques applied to TMA preparations of 1,076 cases of invasive breast cancer to study the combined protein expression profiles of a large panel of well‐characterized commercially available biomarkers related to epithelial cell lineage, differentiation, hormone and growth factor receptors and gene products known to be altered in some forms of breast cancer. Using hierarchical clustering methodology, 5 groups with distinct patterns of protein expression were identified. A sixth group of only 4 cases was also identified but deemed too small for further detailed assessment. Further analysis of these clusters was performed using multiple layer perceptron (MLP)‐artificial neural network (ANN) with a back propagation algorithm to identify key biomarkers driving the membership of each group. We have identified 2 large groups by their expression of luminal epithelial cell phenotypic characteristics, hormone receptors positivity, absence of basal epithelial phenotype characteristics and lack of c‐erbB‐2 protein overexpression. Two additional groups were characterized by high c‐erbB‐2 positivity and negative or weak hormone receptors expression but showed differences in MUC1 and E‐cadherin expression. The final group was characterized by strong basal epithelial characteristics, p53 positivity, absent hormone receptors and weak to low luminal epithelial cytokeratin expression. In addition, we have identified significant differences between clusters identified in this series with respect to established prognostic factors including tumour grade, size and histologic tumour type as well as differences in patient outcomes. The different protein expression profiles identified in our study confirm the biologic heterogeneity of breast cancer and demonstrate the clinical relevance of classification in this manner. These observations could form the basis of revision of existing traditional classification systems for breast cancer. © 2005 Wiley‐Liss, Inc.
Association of two mutations in the CHEK2 gene with breast cancer
Authors: Bogdanova Natalia , Enβen‐Dubrowinskaja Natalia , Feshchenko Sergei , Lazjuk Gennady I. , Rogov Yuri I. , Dammann Olaf , Bremer Michael , Karstens Johann H. , Sohn Christof , Dörk Thilo
Published: April 2005

The 1100delC mutation of the cell cycle checkpoint kinase 2 (CHEK2) gene confers an increased risk for breast cancer, but the clinical impact of other CHEK2 gene variants remains unclear. We determined the frequency of two functionally relevant CHEK2 gene mutations, I157T and IVS2+1G > A, in two large series of breast cancer cases and controls from two independent populations. Our first series consisted of a hospital‐based cohort of 996 German breast cancer cases and 486 population controls, and the second series consisted of 424 breast cancer patients and 307 population controls from the Republic of Belarus. The missense substitution I157T was identified in 22/996 cases (2.2%) vs. 3/486 controls (0.6%; OR = 3.6, 95% CI 1.1–12.2, p = 0.044) in the German population and in 24/424 cases (5.7%) vs. 4/307 controls (1.3%; OR = 4.5, 95% CI 1.6–13.2, p = 0.005) in the Byelorussian cohorts. The splicing mutation IVS2+1G > A was infrequent in both populations, being observed in 3/996 German and 4/424 Byelorussian patients (0.3% and 0.9%, respectively) and in 1/486 German controls (0.2%; adjusted OR = 4.0, 95% CI 0.5–30.8, p = 0.273). Heterozygous CHEK2 mutation carriers tended to be diagnosed at an earlier age in both populations, but these differences did not reach statistical significance. Family history of breast cancer did not differ between carriers and noncarriers. Our data indicate that the I157T allele, and possibly the IVS2+1G > A allele, of the CHEK2 gene contribute to inherited breast cancer susceptibility. © 2005 Wiley‐Liss, Inc.
DNA damage uncouples the mitogenic response to IGF‐I in MCF‐7 malignant breast cancer cells by switching the roles of PI3 kinase and p21WAF1/Cip1
Authors: Clark Martin A. , Perks Claire M. , Winters Zoë E. , Holly Jeff M.P.
Published: April 2005

In addition to its mitogenic and survival actions, recent evidence indicates that IGF‐I can enhance DNA repair, implying IGF activity may limit the efficacy of many therapeutic strategies that rely on induction of DNA damage. Although the individual pathways by which DNA damage and IGF‐I act are well understood, the cross‐talk between these signaling events is not well defined. We examined the effects of DNA damage on the IGF‐I response of MCF‐7 breast cancer cells. Cells were exposed to the UV mimetic, 4‐NQO, or the γ‐irradiation mimetic and chemotherapeutic drug, bleomycin; cellular proliferation was assessed by cell counting, tritiated thymidine incorporation and FACS cell cycle analysis. Although IGF‐I acutely suppressed the p53 response to both agents, it subsequently enhanced the chronic increase in p53 and p21WAF1/Cip1, resulting in cell cycle arrest; however, no apoptosis was observed. Use of specific inhibitors demonstrated that PI3 kinase was utilized with p38 MAPK to induce the p53 response to DNA damage, but was also utilized by IGF‐I to diminish the acute p53 response. In addition, p21WAF1/Cip1 was increased by IGF‐I, which has previously been shown to contribute to the mitogenic response. Here we demonstrate that with DNA damage IGF‐I can also enhance the chronic p53‐dependent increase in p21WAF1/Cip1, culminating in growth arrest. Overall, we have shown that PI3 kinase and p21WAF1/Cip1 play dual roles in mediating the mitogenic response to IGF‐I, but these are both switched by cellular DNA damage to mediate a growth arrest. © 2005 Wiley‐Liss, Inc.
A cluster randomized controlled trial of visual, cytology and human papillomavirus screening for cancer of the cervix in rural India
Authors: Sankaranarayanan Rengaswamy , Nene Bhagwan M. , Dinshaw Ketayun A. , Mahe Cedric , Jayant Kasturi , Shastri Surendra S. , Malvi Sylla G. , Chinoy Roshini , Kelkar Rohini , Budukh Atul M. , Keskar Vijay , Rajeshwarker Raghevendra , Muwonge Richard , Kane Shubhada , Parkin Donald Maxwell
Published: April 2005

The impact of screening by visual inspection with acetic acid (VIA), cytology or HPV testing on cervical cancer incidence and mortality is investigated in a cluster randomized controlled trial in India. We report findings after the screening phase, when 52 clusters, with a total of 142,701 women aged 30–59 years in Osmanabad District, India, were randomized into 4 arms for a single round of screening by trained midwives with either VIA, cytology or HPV testing as well as a control group. All laboratory tests were done locally. Test‐positive women underwent investigations (colposcopy/biopsy) and treatment in the base hospital. Data on participation, test positivity, positive predictive value and detection rates of cervical neoplasia were analyzed using cluster design methodology. Of the eligible women, 72–74% were screened. Test positivity rates were 14.0% for VIA, 7.0% for cytology and 10.3% for HPV. The detection rate of high‐grade lesions was similar in all intervention arms (0.7% for VIA, 1.0% for cytology and 0.9% for HPV testing) (p = 0.06, Mann‐Whitney test). While the detection rate for VIA dropped to 0.5% with declining test positivity during the course of the study, it remained constant for cytology and HPV testing. Over 85% of women with high‐grade lesions received treatment. Our results show that a high level of participation and good‐quality cytology can be achieved in low‐resource settings. VIA is a useful alternative but requires careful monitoring. Detection rates obtained by HPV testing were similar to cytology, despite higher investments. © 2005 Wiley‐Liss, Inc.
Analysis of job‐training effects on Korean women
Authors: Lee Myoung‐jae , Lee Sang‐jun
Published: April 2005

We analyse job‐training effects on Korean women for the period January 1999 to March 2000, using a large data set of size about 52,000. We employ a number of estimation techniques: Weibull MLE and accelerated failure time approach, which are both parametric; Cox partial likelihood estimator, which is semiparametric; and two pair‐matching estimators, which are in essence nonparametric. All of these methods gave the common conclusion that job training for Korean women increased their unemployment duration. The trainings were not cost‐effective in the sense that they took too much time ‘locking in’ the trainees during the training span, compared with the time they took to place the trainees afterwards. Despite this negative finding, some sub‐groups had positive effects: white‐collar workers trained for finance/insurance or information/communication. Copyright © 2005 John Wiley & Sons, Ltd.
I didn't tell, and I won't tell: dynamic response error in the SIPP
Authors: Bollinger Christopher R. , David Martin H.
Published: April 2005

Using state administrative records matched to the 1984 Survey of Income and Program Participation, we examine intertemporal relationships in response errors. False negative errors in reporting food stamps are highly correlated across interviews for the same household. Hypotheses that the error process can be explained by learning behaviour are not supported. Bivariate probit of response error in two periods reveals that responses to covariates are stable over time and the latent error terms are positively correlated. These findings support the hypothesis that respondents have a latent tendency to cooperate (or not cooperate) with surveys. Copyright © 2005 John Wiley & Sons, Ltd.
Translation of STO charge distributions
Authors: Fernández Rico J. , López R. , Ema I. , Ramírez G.
Published: April 2005

Barnett and Coulson's ζ‐function method (M. P. Barnett and C. A. Coulson, Philos. Trans. R. Soc., Lond. A 1951, 243, 221) is one of the main sources of algorithms for the solution of multicenter integrals with Slater‐type orbitals. This method is extended here from single functions to two‐center charge distributions, which are expanded at a third center in terms of spherical harmonics times analytical radial factors. For s–s distributions, the radial factors are given by a series of factors corresponding to the translation of s‐type orbitals. For distributions with higher quantum numbers, they are obtained from those of the s–s distributions by recurrence. After analyzing the convergence of the series, a computational algorithm is proposed and its practical efficiency is tested in three‐center (AB|CC) repulsion integrals. In cases of large basis sets, the procedure yields about 12 correct significant figures with a computational cost of a few microseconds per integral. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 846–855, 2005
Edge‐face chromatic number and edge chromatic number of simple plane graphs
Authors: Luo Rong , Zhang Cun‐Quan
Published: April 2005

Given a simple plane graph G, an edge‐face k‐coloring of G is a function ϕ : E(G) ∪ F(G) →  {1,…,k} such that, for any two adjacent or incident elements a, b ∈ E(G) ∪ F(G), ϕ(a) ≠ ϕ(b). Let χe(G), χef(G), and Δ(G) denote the edge chromatic number, the edge‐face chromatic number, and the maximum degree of G, respectively. In this paper, we prove that χef(G) = χe(G) = Δ(G) for any 2‐connected simple plane graph G with Δ (G) ≥ 24. © 2005 Wiley Periodicals, Inc. J Graph Theory
Retrospective evaluation of the dose of dysport and BOTOX in the management of cervical dystonia and blepharospasm: The REAL DOSE study
Authors: Marchetti Albert , Magar Raf , Findley Leslie , Larsen Jan P. , Pirtosek Zvezdan , Råužižka Evzen , Jech Robert , Sławek Jaroslaw , Ahmed Fayyaz
Published: April 2005

The purpose of this study is to evaluate the real‐world dose utilization of Dysport and BOTOX for cervical dystonia and blepharospasm. Six investigational sites (five countries) were identified. Investigators abstracted utilization data for patients who received Dysport before switching to BOTOX or BOTOX before switching to Dysport. Patients were identified during scheduled clinic visits and selected if they met study criteria, which included treatment for at least 2 consecutive years (at least 1 year with Dysport or BOTOX, then switched and maintained on BOTOX or Dysport for at least another year). A total of 114 patients were included in the assessment. Ratios of mean dose for Dysport to BOTOX ranged from a low of 2:1 to a high of 11:1. Thirty‐one percent of patients fell into the Dysport‐to‐BOTOX ratio grouping of 5:1 to less than 6:1; 30% of patients had a mean ratio of Dysport to BOTOX of 4:1 to less than 5:1; and only 21% of all patients evaluated fell into the Dysport‐to‐BOTOX ratio grouping of 3:1 to less than 4:1. Results are consistent with United Kingdom labeling for botulinum toxins stating that units of different serotype A toxins are not interchangeable and simple dose‐conversion factors are not applicable. © 2005 Movement Disorder Society
Novel movement disorder of the lower lip: Is it epilepsia partialis continua? Clues from a secondary case
Authors: Wali Gurusidheshwar M.
Published: April 2005

A 28‐year‐old woman developed an acute‐onset novel movement disorder of the lower lip mimicking focal dystonia. Investigations showed it to be a presentation of epilepsia partialis continua occurring in association with agenesis of the corpus callosum. It responded favorably to anti‐epileptic drug therapy. Recently, Kleopa and Kyriakides1 reported on 4 patients who developed sudden‐onset movement disorder characterized by a tonic sustained, lateral and outward protrusion of half of the lower lip. They failed to find any causative factors, despite extensive investigation. Treatment with anticholinergics, clonazepam, and botulinum toxin injection failed to improve the movement disorder. I present an additional case of similar focal movement disorder occurring in the presence of agenesis of the corpus callosum. A scalp electroencephalogram revealed focal epileptic activity, and the movement disorder responded favorably to treatment with antiepileptic drugs. © 2005 Movement Disorder Society
Amyloid deposits in transthyretin‐derived amyloidosis: cleaved transthyretin is associated with distinct amyloid morphology
Authors: Bergström Joakim , Gustavsson Åsa , Hellman Ulf , Sletten Knut , Murphy Charles L , Weiss Deborah T , Solomon Alan , Olofsson Bert‐Ove , Westermark Per
Published: April 2005

The pathological fibrillar deposits found in the heart and other organs of patients with senile systemic amyloidosis (SSA) and Swedish familial amyloidotic polyneuropathy (FAP) contain wild‐type (wt) and a mutant form of transthyretin (TTR), respectively. Previously, it was reported that these two forms of amyloid have different molecular features and it was thus postulated that the mechanism responsible for TTR fibrillogenesis in SSA and FAP may differ. To document further the nature of the amyloid in these entities, detailed morphological, histochemical, immunological, and structural analyses of specimens obtained from 14 individuals with SSA and 11 Swedish FAP patients have been performed. Two distinct patterns of amyloid deposition (designated A and B) were evident. In pattern A, found in all SSA and five of 11 FAP cases, the amyloid had a homogeneous but patchy distribution within the sub‐endocardium, sub‐epicardium, and myocardium; exhibited weak congophilia and green birefringence; and was composed of tightly packed, short, unorientated fibrils. This material contained mainly ∼79‐residue C‐terminal fragments of the amyloidogenic precursor protein. In pattern B, seen in the six other FAP patients, the amyloid appeared as thin streaks throughout the cardiac tissue; often surrounded individual muscle cells; was strongly congophilic and birefringent; had long fibrils arranged in parallel bundles, often penetrating into myocytes; and was composed of virtually intact TTR molecules. These findings provide substantive evidence for the morphological and structural heterogeneity of TTR fibrils and suggest that the two types of deposition may reflect fundamental differences in the pathogenesis of the TTR‐associated amyloidoses. Copyright © 2005 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd.
Randomized comparison of antibiotics with and without granulocyte colony‐stimulating factor in children with chemotherapy‐induced febrile neutropenia: A report from the Children's Oncology Group
Authors: Özkaynak M. Fevzi , Krailo Mark , Chen Zhengjia , Feusner James
Published: April 2005

Purpose

To determine if granulocyte colony‐stimulating factor (G‐CSF) with empirical antibiotics accelerates febrile neutropenia resolution compared with antibiotics without it.

Patients and Methods

Eligible children were treated without prophylactic G‐CSF and presented with fever (temperature >38.3°C) and neutropenia afterward. Patients with acute myelogenous leukemia and myelodysplastic syndrome were excluded. Assignments were randomized between G‐CSF (5 μg/kg/day) or none beginning within 24 hr of antibiotics. Subcutaneous administration was recommended, but intravenous G‐CSF was allowed. Patients remained on study until absolute neutrophil count (ANC) >500/μl and ≥48 hr without fever.

Results

One of 67 patients enrolled was ineligible, 59 had acute lymphoblastic leukemia (ALL). Thirty‐four were assigned to antibiotics, 32 to G‐CSF plus antibiotics. Adding G‐CSF significantly reduced neutropenia and febrile neutropenia recovery times. Median days to febrile neutropenia resolution was nine earlier with G‐CSF (4 vs. 13 days) (P < 0.0001). However, there was no difference in the resolution of fever between arms. Hospitalization median was shorter by 1 day with G‐CSF (4 vs. 5 days) (P = 0.04). There was no difference in the duration of IV and oral antibiotic treatment, addition of antifungal therapy, and shock incidence. A trend for decreased incidence of late fever with G‐CSF was noted (6.3 vs. 23.5%) (P = 0.08).

Conclusions

Adding G‐CSF to empiric antibiotic coverage accelerates chemotherapy‐induced febrile neutropenia resolution by 9 days in pediatric patients, mainly with ALL, which results in a small but significant difference in the median length of hospitalization. © 2005 Wiley‐Liss, Inc.
Symptoms of post‐traumatic stress in children with cancer and their parents: Effects of informant and time from diagnosis
Authors: Phipps Sean , Long Alanna , Hudson Melissa , Rai Shesh N.
Published: April 2005

Background

Post‐traumatic stress disorder (PTSD) has been put forth as a model for understanding the adjustment of children with cancer and their parents, but findings in the literature regarding the prevalence of post‐traumatic stress symptoms (PTSS) have been mixed. This study examined PTSS levels in both patients and parents as a function of time elapsed from diagnosis, and by use of parent versus child reports for assessing patient PTSS.

Procedure

Four groups of patients (total N = 162) differing in time elapsed since diagnosis were assessed with standardized measures of PTSS. Patients reported on their own symptoms, while parents reported on their symptoms as well as symptoms in their child.

Results

Significant differences between groups were observed on all patient PTSS measures. Recently diagnosed patients obtained higher PTSS scores than survivors more than 5 years from diagnosis. Likewise, parents of recently diagnosed patients self‐reported significantly higher levels of PTSS than parents of long‐term survivors. Parent–child correlations were high and no differences were observed between parent and patient report of patient PTSS. Comparison with historical control data suggests that levels of PTSS in patients are very low.

Conclusion

Concordance between parent and child reports of child PTSS suggests that data may be obtained with reasonable confidence from either if only one informant is available. Higher levels of PTSS in patients who are recently diagnosed (and their parents) in comparison to long‐term survivors, suggest that the symptoms reported reflect primarily a concurrent response to ongoing acute stressors, rather than a post‐traumatic re‐experiencing of past traumas. This, in combination with the low levels of patient PTSS raise questions regarding the utility of PTSD as a model for understanding patient and parent adjustment to childhood cancer. © 2005 Wiley‐Liss, Inc.
Clotting times and tensile properties of insoluble silk fibroin films containing heparin
Authors: Lv Qiang , Cao Chuanbao , Zhu Hesun
Published: April 2005

Although many novel approaches for producing small‐caliber arterial grafts have been developed, problems with mechanical properties and blood compatibility have up to now prevented clinical implementation. Blending anticoagulant agents with natural biomaterials having excellent cell attachment and growth properties, and making the release time of anticoagulant agents exceed the time required by endothelial tissue regeneration, might be a novel method to prepare appropriate biomaterials used in small‐diameter arterial grafts. In this article, an insoluble fibroin film, having excellent blood compatibility and mechanical properties, was obtained by blending with heparin. The structural properties of the films were examined through Fourier‐transform infrared attenuated total reflectance (FTIR‐ATR) and X‐ray diffraction (XRD). The results indicated that plentiful β‐sheet crystals existed in fibroin films containing heparin. The tensile strength and elongation at break of film containing heparin were, respectively, 10.3 MPa and 54 % in the wet state, which can satisfy the mechanical requirements of blood‐contacting materials such as small‐diameter tubing. The clot times [activated partial thromboplastin time (APTT), thrombin time (TT) and prothrombin time (PT)] all exceeded the measurement limit of the clot detection instrument. Even the APTT and TT of film immersed in water for 28 days exceeded the measurement limit of the clot detection instrument. The in vitro culture of endothelial cells on the film was also investigated, and the result indicated that cells can grow to cover all of the available surface area of the film within 8 days. Fibroin films containing heparin could retain blood compatibility for 28 days, which means that this is a promising material for small‐diameter artery applications. Copyright © 2005 Society of Chemical Industry
Bridging the gap between research and practice: A framework for building research agendas in school psychology
Authors: Riley‐Tillman T. Chris , Chafouleas Sandra M. , Eckert Tanya L. , Kelleher Constance
Published: April 2005

In this article, we discuss the history behind efforts to transfer school psychology research into practice and review the literature pertaining to treatment acceptability, participatory action research, organizational change, and generalization programming. We then present a model for the systematic programming of this transfer and propose a three‐step framework that emphasizes multiple conceptual bases to transfer research into practice. This three‐step framework includes creating usable knowledge, transferring usable knowledge, and supporting usable knowledge. It is our intention that the proposed framework will provide a starting point that can be informed by researchers and practitioners in the field of school psychology. We conclude with examples of our research efforts to systematically study the transfer of research into practice. © 2005 Wiley Periodicals, Inc. Psychol Schs 42: 459–473, 2005.
Synthesis and photophysical properties of polyfluorenes bearing silicon‐based functional groups
Authors: Takagi Koji , Kunii Satoshi , Yuki Yasuo
Published: April 2005

Five polyfluorenes bearing bulky trimethylsilyl (PTMS1 and PTMS2), tris(trimethylsilyl)silyl (PTTMS1), and silsesquioxane groups (PPOSS1 and PPOSS2) were synthesized through palladium‐catalyzed Suzuki coupling reactions. In the solution state, every polymer showed comparable ultraviolet–visible spectra, and they emitted blue light with high quantum efficiency. In the solid state, however, three trimethylsilyl‐functionalized polyfluorenes indicated redshifts of the fluorescence peak. In particular, PTMS1 and PTTMS1, having a hydrogen at the C‐9 position of fluorene, also showed green‐light emissions. After the annealing of the spin‐coated films, the blue‐emissive peak decreased and the green‐emissive peak became stronger in the photoluminescence spectra of three trimethylsilyl‐functionalized polyfluorenes. In contrast, PPOSS2 showed a pure blue‐light emission in the film state and even after the thermal treatment, which could be accomplished by the encapsulation of the polymer chains by the large polyhedral oligomeric silsesquioxane molecule. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2119–2127, 2005