bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient methods for the synthesis of 5‐(4‐[18F]fluorophenyl)‐10,15,20‐tris(3‐methoxyphenyl)porphyrin as a potential imaging agent for tumor
Authors: Kavali Rajesh R. , Chul Lee Byung , Seok Moon Byung , Dae Yang Seung , Soo Chun Kwon , Woon Choi Chang , Lee Chang‐Hee , Yoon Chi Dae
Published: July 2005

F‐18‐labeled porphyrins, the potential tracing and detecting agents for tumor have been synthesized and characterized by two convenient routes: one is a mixed aldehyde condensation, which involves acid‐catalyzed condensation of pyrrole, m‐anisaldehyde and 4‐[18F]fluorobenzaldehyde. The other is the acid‐catalyzed condensation of tetrapyrrane with 4‐[18F]fluorobenzaldehyde. The synthetic methodologies including solvents, reaction concentrations and catalysts are optimized for radiolabeled porphyrins. The methods also provide the desired product in reasonable radiochemical yield (20–26%) compared with those of cold chemical synthesis (1–3%) and with high radiochemical purity (>95%). The methods described here would be effective and convenient ways to produce radiolabeled porphyrin. Copyright © 2005 John Wiley & Sons, Ltd.
Microscale synthesis of isotopically labeled 6R‐N5, N10 methylene‐5, 6, 7, 8‐tetrahydrofolate
Authors: Hong Baoyu , Kohen Amnon
Published: July 2005

A one‐pot chemo‐enzymatic microscale synthesis of isotopically labeled R‐[6‐YH; 11‐XH] N5, N10 methylene‐5, 6, 7, 8‐tetrahydrofolate (CH2H4folate) is presented, where Y=1 or 2 represents protium or deuterium, and X=1, 2 or 3 represents protium, deuterium or tritium, respectively. In this procedure, Thermoanaerobium brockii alcohol dehydrogenase (tbADH) and Escherichia coli dihydrofolate reductase (ecDHFR) were used simultaneously in the reaction mixture. First, tbADH stereospecifically catalyzes a hydride transfer from [2‐YH] iPrOH to the re face of C‐4 NADP+. The ecDHFR then reduced 7, 8‐dihydrofolate (H2folate) to form (6S)‐H4folate. Finally, the enzymatic reactions were followed by chemical trapping with isotopically labeled formaldehyde ([XH]‐HCHO) to form the final product. The preparation of deuterium‐ and tritium‐labeled formaldehyde is also presented. Two reverse phase HPLC methods were developed for analysis and purification of product R‐[6‐YH; 11‐XH] CH2H4folate. This isotopically labeled cofactor can be used to study 1° and 2° kinetic isotope effects (KIEs) with any CH2H4folate dependent enzyme as demonstrated by studies with E. coli thymidylate synthase (TS). Copyright © 2005 John Wiley & Sons, Ltd.
Synthesis of [18F]fluoroalkyl esters of carfentanil
Authors: Henriksen Gjermund , Herz Michael , Schwaiger Markus , Wester Hans‐Jürgen
Published: July 2005

With the aim to develop and evaluate new ligands for depicting the µ‐opioid receptor with positron emission tomography, the 18F‐fluoroalkyl esters of carfentanil, 3‐carboxy‐(2‐[18F]fluoroethyl)fentanyl, (2‐[18F]fluoroethyl‐carfentanil) and 3‐carboxy‐(3‐[18F]fluoropropyl)fentanyl (3‐[18F]fluoropropyl‐carfentanil) were prepared by a two‐step radiosynthesis. Reacting carfentanil carboxylate sodium salt, added 0.96 eqv. of tetrabutyl ammonium hydroxide (TBAH), with no‐carrier‐added (n.c.a.) 2‐[18F]fluoroethyltosylate for 20 min at 150°C in dimethyl formamide (DMF) provided 2‐[18F]fluoroethyl carfentanil in an isolated radiochemical yield (RCY) of 36 ± 8%, a specific activity (SA) of 35 ± 5 TBq/mmol (n=4) within a synthesis time of ∼100 min. Similarly, 3‐[18F]fluoropropyl carfentanil could be obtained by reacting the carfentanil TBA/Na salt with 3‐[18F]fluoropropyl iodide at 160°C in DMF (isolated RCY=6 ± 2%; ∼100 min, SA=27 ± 5 TBq/mmol, n=4). The developed methods allow the production of the two 18F‐labeled carfentanil derivatives in amounts and specific activities necessary and relevant for a detailed preclinical evaluation of these new potential µ‐opioid receptor ligands in vitro and in animal models. Copyright © 2005 John Wiley & Sons, Ltd.
The neuroprotective KDI domain of γ1‐laminin is a universal and potent inhibitor of ionotropic glutamate receptors
Authors: Möykkynen Tommi , Liebkind Ron , Sjöberg Jari , Korpi Esa R. , Liesi Päivi
Published: July 2005

Previous work from this laboratory indicates that the KDI (Lys‐Asp‐Ile) domain of γ1‐laminin promotes functional regeneration of adult rat spinal cord injuries and protects adult rat hippocampal neurons against massive neuronal death induced by intracerebral injection of the glutamate analogue kainic acid. In the present study, we used patch clamp recordings on cultured human embryonic neocortical neurons and HEK 293 cells expressing recombinant glutamate receptor subunits to study a putative interaction of the KDI with the glutamate system. We show that the KDI domain of γ1‐laminin is a universal and potent inhibitor of AMPA, kainate, and NMDA subclasses of glutamate receptors, with a noncompetitive action on the AMPA receptor channel activity. Glutamate neurotoxicity plays a key role in both CNS trauma and neurodegenerative disorders, so this unexpected, novel function of the γ1‐laminin‐derived tripeptide may prove clinically valuable in treatment of CNS trauma and/or disease. © 2005 Wiley‐Liss, Inc.
Two‐stage dilute acid‐catalyzed hydrolytic conversion of softwood sawdust into sugars fermentable by ethanologenic microorganisms
Authors: Kim Kyoung Heon
Published: July 2005

Softwood hemlock residues generated in a sawmill were tested as a feasible agricultural feedstock for the production of high‐value bio‐based products using the concept of two‐stage dilute acid hydrolysis. To convert the carbohydrate contained in the hemlock sawdust, two‐stage dilute‐acid catalyzed hydrolysis was conducted. In the first stage, sawdust was hydrolyzed at 190 °C for 150 s with 1.1wt% sulfuric acid and 46.0 wt% total solids. As a result, 69.3% mannose, 74.2% galactose, 67.7% xylose, and 17.4% glucose of their theoretical maximum yields were achieved, which reveals that hemicellulose was the major target in the first‐stage hydrolysis. After recovering soluble sugars by washing from the first‐stage hydrolysate with water, the washed first‐stage hydrolysate solids were hydrolyzed again in the second stage at more severe conditions, such as 2.6 or 3.5 wt% H2SO4, 205 or 210 °C, and 80–135 s. After the two stages, the highest overall yields from 100 g of dry hemlock sawdust were a total of 39.3 g of fermentable sugars (36.0 and 3.3 g of hexose and pentose sugars, respectively). These results indicate that hemlock sawdust could be used to produce fermentable sugars which can be converted into other value‐added bio‐based products. Copyright © 2005 Society of Chemical Industry
Southern French thyme oils: chromatographic study of chemotypes
Authors: Kaloustian Jacques , Abou Lydia , Mikail Céline , Amiot Marie J , Portugal Henri
Published: July 2005

Oils obtained from seven chemotypes (thymol, linalool, geraniol, borneol, (E)‐sabinene hydrate/terpinene‐4‐ol, p‐cymene and carvacrol) of Thymus vulgaris (thyme) that exist in the South of France were analysed by gas chromatography/mass spectrometry (GC/MS) and characterised. Wild thyme growing in three departments (Bouches du Rhone, Var and Vaucluse) of Provence and in a fourth neighbouring department (Gard) was also studied. This is often the result of a mixture of three chemotypes: thymol, carvacrol and p‐cymene. Linalool and (E)‐sabinene hydrate/terpinene‐4‐ol were observed as minor chemotypes. GC/MS was also used to monitor seasonal variations in the composition of the oil obtained from thyme harvested at the same location (Gemenos, near Marseille, Bouches du Rhone) during the plant vegetative and life cycles (19 samples). Four components were determined: the phenols thymol and carvacrol and the monoterpene hydrocarbon precursors p‐cymene and γ‐terpinene. Results showed maximum oil (34.1 mL kg−1 dry matter) and phenolic terpenoid (95.4 mmol kg−1 dry matter) contents occurring in May, the period of flowering and harvesting. In contrast, in December the oil displayed a higher level of phenolic precursors (p‐cymene and γ‐terpinene, 72.8 mmol kg−1 dry matter) than phenolic terpenoids. Depending on the harvesting date, the oils isolated from southern French thyme (T. vulgaris) could have different potential biological activities. Copyright © 2005 Society of Chemical Industry
Inhibition of epidermal growth factor‐induced cell transformation and Akt activation by caffeine
Authors: Nomura Masaaki , Ichimatsu Daisuke , Moritani Shuzo , Koyama Ichiko , Dong Zigang , Yokogawa Koichi , Miyamoto Ken‐ichi
Published: July 2005

We found that caffeine significantly inhibited epidermal growth factor (EGF)‐ and 12‐O‐tetradecanoylphorbol‐13‐acetate (TPA)‐induced cell transformation in the JB6 mouse epidermal cell line. The tumor promoter‐induced cell transformation was also blocked by treatment with an adenosine A1 receptor antagonist, 8‐phenyltheophylline (8‐PTH). Caffeine slightly attenuated activation of EGF‐induced activator protein 1 (AP‐1) activation, which play important roles in cell transformation, but only at the highest concentration examined (1 mM). Interestingly, pretreatment with caffeine suppressed EGF‐induced phosphorylation and activation of Akt and ribosomal p70 S6 protein kinase (p70 S6K), a target of Akt, without inhibiting phosphatidylinositol 3‐kinase (PI3K) activation. The inhibition of Akt activation of caffeine was not a result of its adenosine receptor antagonism. Because Akt plays a key role in signal transduction pathways leading to cell proliferation and apoptosis, our results provide novel insight into possible mechanisms of the chemotherapeutic effect of caffeine. © 2005 Wiley‐Liss, Inc.
Inhibition of the Akt, cyclooxygenase‐2, and matrix metalloproteinase‐9 pathways in combination with androgen deprivation therapy: Potential therapeutic approaches for prostate cancer
Authors: Miyamoto Hiroshi , Altuwaijri Saleh , Cai Yi , Messing Edward M. , Chang Chawnshang
Published: July 2005

Prostate cancer cells are generally dependent on androgen stimulation mediated by the androgen receptor (AR) for growth and survival, and, therefore, hormonal manipulation, such as castration and/or the use of AR antagonists, results in a regression of the cancer. However, this treatment very rarely leads to the “cure” of advanced disease, and cancers eventually become androgen‐independent. A number of genes/pathways have been reported to be activated in prostate cancer, most of which are possibly associated with disease progression. In this article, among them, we focus on Akt (also known as protein kinase B), cyclooxygenase (COX)‐2, and matrix metalloproteinase (MMP)‐9, whose activities or expressions have been found to be regulated by androgens/AR. Previous studies by us and others, with androgen‐sensitive prostate cancer cell lines, have demonstrated that androgen deprivation results in activation/overexpression of Akt, COX‐2, and MMP‐9 in cells. This suggests that androgen deprivation in clinical settings activates the Akt, COX‐2, and MMP‐9 pathways in prostate cancer, which may increase cell growth and in turn promote the transition to the androgen‐independent state. We hypothesize that androgen deprivation, in combination with inhibition of the Akt, COX‐2, and MMP‐9 pathways, delays the androgen‐independent transition and has more beneficial effects than hormonal therapy alone. © 2005 Wiley‐Liss, Inc.
Inhibition of TPA‐induced cyclooxygenase‐2 (COX‐2) expression by apigenin through downregulation of Akt signal transduction in human keratinocytes
Authors: Van Dross Rukiyah T. , Hong Xiaoman , Pelling Jill C.
Published: July 2005

Apigenin is a nonmutagenic bioflavonoid that has been shown to be an inhibitor of mouse skin carcinogenesis induced by the two‐stage regimen of initiation and promotion with dimethylbenzanthracene (DMBA) and 12‐O‐tetradecanoylphorbol‐13‐acetate (TPA). These DMBA/TPA‐induced squamous cell carcinomas overexpress cyclooxygenase‐2 (COX‐2). Cyclooxygenases are key enzymes required for prostaglandin (PG) synthesis, converting the arachidonic acid (AA) released by phospholipase A2 into prostaglandins. A large body of evidence indicates that the inducible form of cyclooxygenase, COX‐2, is involved in tumor promotion and carcinogenesis in a wide variety of tissue types, including colon, breast, lung, and skin. In the present study, we have determined that apigenin inhibited the TPA‐induced increase in COX‐2 protein and mRNA in the human keratinocyte cell line; HaCaT. The induction of COX‐2 elicited by TPA correlated with increased activation of Akt kinase and cell treatment with the PI3 kinase inhibitor, LY294002, blocked TPA induction of COX‐2. In cells treated with TPA and apigenin, the inhibition of COX‐2 expression correlated with inhibition of Akt kinase activation. Apigenin‐mediated inhibition of TPA‐induced COX‐2 expression was reversed by transient transfection with constitutively active Akt (CA‐Akt). Chemical inhibitors of MEK (PD98059), p38 (SB202190), but not JNK (SP600125) blocked TPA induction of COX‐2 although apigenin did not inhibit TPA‐mediated COX‐2 expression through these pathways. The TPA‐induced release of AA from HaCaT cells was also inhibited by cell treatment with apigenin. These data show that apigenin inhibits TPA‐mediated COX‐2 expression by blocking signal transduction of Akt and that apigenin also blocks AA release, which may contribute to its chemopreventive activity. © 2005 Wiley‐Liss, Inc.
Differential gene expression in epidermis of mice sensitive and resistant to phorbol ester skin tumor promotion
Authors: Riggs Penny K. , Angel Joe M. , Abel Erika L. , DiGiovanni John
Published: July 2005

Previous data from two‐stage carcinogenesis studies in mouse skin demonstrated that genetic control of susceptibility to skin tumor promotion by the phorbol ester, 12‐O‐tetradecanoylphorbol‐13‐acetate (TPA), in crosses between susceptible DBA/2J and resistant C57BL/6J mice is a multigenic trait. Utilizing a cDNA microarray approach, we compared global gene expression profiles in the epidermis of these two mouse strains treated with TPA or vehicle (acetone). Gene expression in the epidermis was analyzed after the treatment to identify global effects of TPA, as well as potential candidate genes that modify susceptibility to skin tumor promotion. DBA/2J and C57BL/6J mice were treated topically four times with 3.4 nmol TPA or acetone over a 2‐wk period, and RNA was extracted from epidermis 6 h after the final treatment. Labeled cDNA generated from each group was hybridized to commercial cDNA microarrays (Agilent) containing more than 8000 targets. More than 450 genes were significantly influenced, directly or indirectly, by TPA treatment in the epidermis of either strain. Notably, 44 genes exhibited differential expression between the tumor promotion sensitive and resistant mouse strains. Several genes that were differentially expressed in DBA/2J versus C57BL/6J epidermis after TPA treatment were located in chromosomal regions linked to TPA promotion susceptibility. Three genes, Gsta4, Nmes1 (MGC58382), and Serpinb2, located within promotion susceptibility loci Psl1 (chr 9), Psl2 (chr 2), and Psl3 (chr 1), respectively, were identified in this analysis as potential candidates for modifiers of susceptibility to skin tumor promotion by TPA. © 2005 Wiley‐Liss, Inc.
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 , Růžička Evžen , Jech Robert , Sławek Jaroslaw , Ahmed Fayyaz
Published: July 2005

The original article to which this Erratum refers has been published in Movement DisordersMov Disord (2005) 20 (8) 937–934. © 2005 Movement Disorder Society
Non‐greedy heuristics and augmented neural networks for the open‐shop scheduling problem
Authors: Colak Selcuk , Agarwal Anurag
Published: July 2005

In this paper we propose some non‐greedy heuristics and develop an Augmented‐Neural‐Network (AugNN) formulation for solving the classical open‐shop scheduling problem (OSSP). AugNN is a neural network based meta‐heuristic approach that allows integration of domain‐specific knowledge. The OSSP is framed as a neural network with multiple layers of jobs and machines. Input, output and activation functions are designed to enforce the problem constraints and embed known heuristics to generate a good feasible solution fast. Suitable learning strategies are applied to obtain better neighborhood solutions iteratively. The new heuristics and the AugNN formulation are tested on several benchmark problem instances in the literature and on some new problem instances generated in this study. The results are very competitive with other meta‐heuristic approaches, both in terms of solution quality and computational times. © 2005 Wiley Periodicals, Inc. Naval Research Logistics, 2005.
Optimising communications for charity brand management
Authors: Jenkinson Angus , Sain Branko , Bishop Kevin
Published: July 2005

The paper presents recomendations on how to enhance communications planning through new integration and media neutral planning techniques (open planning) linked to Integrated Marketing practice. The paper is based on best practice research in charity and commercial sectors, including NSPCC and National Trust. Copyright © 2005 John Wiley & Sons, Ltd.
The face and voice of volunteering: a suitable case for branding?
Authors: Hankinson Philippa , Rochester Colin
Published: July 2005

Volunteers make a substantial contribution to UK society but the level of volunteering has peaked and may, in part, be due to the poor ‘image’ of volunteering. Through qualitative research, this study explores the need to re‐shape perceptions of volunteering and the extent to which this may be achieved through branding. Key findings suggest that although there is much consistency in perceptions about generic volunteering, perceptions of the different strands of volunteering, such as governance and campaigning, are different and may require individual development as sub‐brands. It is argued that Volunteering England is best placed to lead a brand development programme, supported by managers of national and local bodies as well as volunteers to create a new visual identity and, importantly, key messages that will resonate with current and potential volunteers across different areas of activity. Copyright © 2005 John Wiley & Sons, Ltd.
Valuing not‐for‐profit and charity brands—real insight or just smoke and mirrors
Authors: Haigh David , Gilbert Stephen
Published: July 2005

Brands introduce emotional decision‐making criteria, differentiating all brands across the not‐for‐profit sector. Brands shift the demand curve upwards and the cost curve downwards. The result is higher turnover, profit and surplus ‘consumer utility’. Brand equity is a measure of the emotional reservoir that shows how far the demand curve has moved and what the future cash flows will be. Brand valuation is a snapshot of those future cash flows. David Haigh and Stephen Gilbert's article describes how these three concepts fit together and explains how and why they have become best practice in marketing and financial management. Copyright © 2005 John Wiley & Sons, Ltd.
Building and rebuilding charity brands: the role of creative agencies
Authors: Griffiths Mark
Published: July 2005

People who work in creative agencies tend to see a charitable organisation as a brand like any in the commercial world, and rightly so. While this is the correct starting point, there is often a huge gap between this simple understanding and the ability to deliver the changes in perception and behaviour that charities need. Besides strict governance and the obvious need for transparency and integrity, charity brands face many other issues, whether rebuilding or starting from scratch. They exist mainly to solve problems, not to meet a demand. Understanding this very different raison d'etre is the second greatest hurdle that creative agencies have to overcome when working on charity brands. The greatest is getting the charity to consider itself a brand and all that entails. When charities get beyond their complacency and suspicion and creative agencies their arrogance and superficiality—as with Breakthrough Breast Cancer and the Fairtrade Foundation—these two obstacles can be overcome. Copyright © 2005 John Wiley & Sons, Ltd.
Fabrication of poly(2‐oxy‐6‐naphthoyl) particles by direct polycondensation of 2‐hydroxy‐6‐naphthoic acid
Authors: Kimura Kunio , Horii Toshiyuki , Kohama Shin‐ichiro , Yamashita Yuhiko
Published: July 2005

Morphology control of poly(2‐oxy‐6‐naphthoyl) (PON) was examined by using reaction‐induced crystallization of oligomers during direct polycondensation of 2‐hydroxy‐6‐naphthoic acid with p‐toluenesulfonyl chloride and N,N‐dimethylformamide in pyridine. PON particles were obtained of which the diameter was in the range of 8.0–8.3 µm. The particles were comprised of many lamellae and exhibited spherulitic morphology. They possessed high crystallinity evaluated from wide‐angle X‐ray scattering (WAXS). Formation mechanism of the particles was clarified from the results of morphology observation, yield, density and WAXS. When the number average degree of polymerization of the oligomers exceeded a critical value of ca. 4–5, they were precipitated to form lamellae. The lamellae grew to spherulites through screw dislocation with continuous precipitation of the oligomer from the solution. Finally, further polymerization occurred gradually in the precipitates. Copyright © 2005 John Wiley & Sons, Ltd.
Solubilization of fullerene into ionic liquids by the use of fluoroalkyl end‐capped oligomers
Authors: Sawada Hideo , Kasai Remi
Published: July 2005

Fluoroalkyl end‐capped oligomers were solubilized into a variety of ionic liquids such as N‐methylpyrazolium tetrafluoroborate, 3‐methylpyrazolium tetrafluoroborate and 1‐butyl‐3‐methylimidazolium hexafluorophosphate, and these fluorinated oligomers were able to reduce the surface tension of these ionic liquids. Interestingly, these fluorinated oligomers were able to solubilize fullerene into ionic liquids effectively. Fluoroalkyl end‐capped fullerene co‐oligomers, which were prepared by the oligomerizations of fluoroalkanoyl peroxides with radical polymerizable monomers such as acryloylmorpholine in the presence of fullerene, were more effective in solubilizing fullerene into ionic liquids compared to the corresponding fluoroalkyl end‐capped homo‐oligomers possessing no fullerene units. Fluoroalkyl end‐capped fullerene co‐oligomers/fullerene/ionic liquid complexes thus obtained were applied to the arrangements of fullerenes above the poly(methyl methacrylate) (PMMA) surface, and the higher fluorescent intensity of fullerene was obtained in the modified PMMA surface, although the reverse side of this modified film surface afforded an extremely weak fluorescent intensity. Copyright © 2005 John Wiley & Sons, Ltd.
Preparation of novel organic‐inorganic nanoporous membranes
Authors: Sasaki Takafumi , Nagaoka Shoji , Tezuka Teppei , Suzuki Yoshiaki , Iwaki Masaya , Kawakami Hiroyoshi
Published: July 2005

In this study, the water permeability, the rejection property of sucrose and glucose, the fouling property of humic acid as the foulant for a novel porous fluorinated polyimide membrane made by combining the ion irradiation and plasma treatment have been reported. First, an asymmetric polyimide membrane with a defect‐free and thin skin layer was prepared, then ions on the skin layer were irradiated and the ion‐irradiated layer was treated by plasma to form nanopores in the layer. The asymmetric polyimide membranes with a defect‐free skin layer were irradiated with 50 keV He+ at 1 × 1015 ions/cm2, and the irradiated polyimide surfaces were treated by Ar glow discharge. The porous polyimide membrane showed a high water flux and excellent rejection properties and fouling resistance when compared with NTR‐7250, which is commercially available. These findings indicated that the pore size formed on the porous polyimide membrane was effectively controlled by the plasma treatment time and the skin layer thickness. Copyright © 2005 John Wiley & Sons, Ltd.
Cobaltporphyrin‐adsorbed carbon black: highly efficient electrocatalysts for oxygen reduction
Authors: Yuasa Makoto , Yamaguchi Aritomo , Oyaizu Kenichi , Fujito Yosuke , Kitao Mizuki , Sato Tsuyoshi
Published: July 2005

meso‐Substituted cobalt porphyrins adsorbed on carbon black were prepared as catalysts for the electroreduction of O2. The catalyst, which was prepared by using a homogenizer in mixing cobalt tetraethylporphyrin and carbon black, gave rise to electroreduction of O2 at a remarkably positive potential (Ep = 0.45 V versus saturated calomel electrode (SCE)) and showed a high selectively for the four‐electron reduction (n = 3.8). Electrochemical study and extended X‐ray absorption fine structure (EXAFS) analysis revealed that the adsorbed face‐to‐face dimeric aggregates of cobalt porphyrin molecules were highly efficient catalysts for electroreduction of O2. Copyright © 2005 John Wiley & Sons, Ltd.
Deuterium solid echo line shape study of poly(ethylene oxide) dynamics in a blend with poly(methyl methacrylate)
Authors: Cao Haihui , Lin Guoxing , Jones Alan A.
Published: July 2005

Deuterium solid echo line shapes were measured on deuterated poly(ethylene oxide) (d4PEO) in a blend with protonated poly(methyl methacrylate) to characterize chain dynamics of this component in the blend. Line shapes were observed as a function of temperature from 183 to 243 K and echo delay times from 10 to 100 μs on a blend containing 20 wt % d4PEO. The line shapes and the associated relative intensities were quantitatively interpreted in terms of segmental motion and libration. The results of the interpretation are compared to an earlier study of deuterium spin‐lattice relaxation times over the temperature range of 313 to 413 K. A combined interpretation of both sets of data is developed based on bimodal distribution of correlation times that are separated by about 2 orders of magnitude in time. The faster mode is 30% of the correlation function with a stretched exponent near one while the slower mode is characterized by an exponent of 0.5. The source of the bimodal character is not revealed by the line shape and relaxation data but is consistent with the presence of two glass transition temperatures in this miscible blend and anomalous translational diffusion of diethyl ether through the blend. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2433–2444, 2005
A mesoscopic Archimedean tiling having a new complexity in an ABC star polymer
Authors: Takano A. , Kawashima W. , Noro A. , Isono Y. , Tanaka N. , Dotera T. , Matsushita Y.
Published: July 2005

The Archimedean tiling (32.4.3.4) is a regular but complex polygonal assembly of equilateral triangles and squares. This tiling pattern with mesoscopic repeating distance has been found for an ABC star‐branched three‐component polymer composed of polyisoprene, polystyrene, and poly(2‐vinylpyridine). In this structure the environment of a molecule splits into multiple sites and two microdomains with different sizes and shapes are formed for one component. This complexity is the first observation in complex polymer systems and can lead to a new type of mesoscale self‐organization. The tiling pattern has been observed for the other materials on much shorter length‐scale; therefore, the experimental fact observed in the present study is demonstrating that the complexity is universal over different hierarchies. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2427–2432, 2005
An open‐label study of the effects of bupropion SR on fatigue, depression and quality of life of mixed‐site cancer patients and their partners
Authors: Moss Erin L. , Simpson J. Steven A. , Pelletier Guy , Forsyth Peter
Published: July 2005

This preliminary study investigated whether bupropion sustained release (SR) improved symptomatic fatigue, depression and quality of life in cancer patients and caregiver quality of life. The sample consisted of a prospective open case series of 21 cancer patients, with fatigue and with or without depression at moderate to severe levels, referred for psychiatric assessment from a tertiary care cancer centre. Both patient symptom ratings and caregiver ratings were measured before and after 4 weeks of treatment with the maximally tolerated dose of bupropion in the range of 100–300 mg per day. At trial completion, significant improvement was found for symptoms of fatigue and depression. Subjects were divided into two groups: depressed and non‐depressed (based on a cut‐off score of 17 on the Hamilton Depression Rating Scale). Both groups reported improvement for fatigue and depressive symptoms. Depressed subjects and their caregivers did not experience any change in quality of life, while the non‐depressed subjects and their caregivers reported improvements. Results from this small group of patients suggest that bupropion may have potential as an effective pharmaceutical agent for treating cancer‐related fatigue. A randomized, placebo‐controlled trial with this medication is indicated. Copyright © 2005 John Wiley & Sons, Ltd.
Stability of decisional role preference over the course of cancer therapy
Authors: Mallinger Julie B. , Shields Cleveland G. , Griggs Jennifer J. , Roscoe Joseph A. , Morrow Gary R. , Rosenbluth Richard J. , Lord Raymond S. , Gross Howard
Published: July 2005

Cancer patients vary in their preferred level of involvement in medical decision making, and responding to patients' desired level of involvement is a key element of good medical care. While the literature has clearly demonstrated heterogeneity among cancer patients' preferences, less is known about how the preferences of any given patient may change over time. This longitudinal study compared cancer patients' preferences for involvement in medical decision making from the time of diagnosis to the time of completion of therapy. Data from 729 cancer patients with mixed diagnoses were analyzed. Most patients reported a change in preferred level of involvement over time, and multivariate analysis demonstrated that patients tend to prefer a decreasing level of involvement over time (p<0.0001). Stability of patients' preferences was also associated with type of cancer, but not with other sociodemographic characteristics. The results from this study highlight the importance of reevaluating patients' preferences for involvement in medical decision making throughout the course of cancer therapy, as such preferences are likely to change. Copyright © 2005 John Wiley & Sons, Ltd.
Cancer‐related health worries and psychological distress among older adult, long‐term cancer survivors
Authors: Deimling Gary T. , Bowman Karen F. , Sterns Samantha , Wagner Louis J. , Kahana Boaz
Published: July 2005

While long‐term survivors (5 years+) do not face the stressors of diagnosis and treatment, they continue to face the uncertainties that survivorship brings: recurrence, other cancers, late effects of treatment, and the potential of a shortened life expectancy. This research focuses on the cancer‐related health worries of older adult, long‐term cancer survivors, the factors that predict these worries, and their link to traditional measures of psychological distress. Specifically, a model is proposed that identifies the personal (including race and gender) and illness/treatment characteristics of survivors that are significantly associated with cancer‐related health worries and their effects on anxiety and depression. Descriptive and multivariate analyses of a random sample of 321 long‐term survivors in a major cancer center tumor registry are used to address these issues. About one‐third of survivors continue to report worries about recurrence, worries about a second cancer, and worries that symptoms they experience may be from cancer. The regression analyses show that cancer‐related health worries is a significant predictor of both depression (beta=0.36) and anxiety (beta=0.21). Race is a significant predictor; being African American is related to fewer cancer‐related health worries (beta=−0.22). Having more symptoms during treatment is also a predictor of having more cancer‐related health worries (beta=0.20). The most consistent predictor of psychosocial distress is dispositional optimism/pessimism, with more optimistic individuals reporting fewer cancer‐related health worries (beta=−0.27), lower levels of both anxiety (beta=−0.16) and depression (beta=−0.23). Overall, for many older adult, long‐term survivors, the legacy of cancer continues in terms of cancer‐related health worries. In spite of these, for most survivors, their quality of life is not dramatically compromised either physically or psychologically. Copyright © 2005 John Wiley & Sons, Ltd.
Interactions of macromolecules with salt ions: An electrostatic theory for the Hofmeister effect
Authors: Zhou Huan‐Xiang
Published: July 2005

Salting‐out of proteins was discovered in the nineteenth century and is widely used for protein separation and crystallization. It is generally believed that salting‐out occurs because at high concentrations salts and the protein compete for solvation water. Debye and Kirkwood suggested ideas for explaining salting‐out (Debeye and MacAulay, Physik Z; 1925;131:22–29; Kirkwood, In: Proteins, amino acids and peptides as ions and dipolar ions. New York: Reinhold; 1943. p 586–622). However, a quantitative theory has not been developed, and such a theory is presented here. It is built on Kirkwood's idea that a salt ion has a repulsive interaction with an image charge inside a low dielectric cavity. Explicit treatment is given for the effect of other salt ions on the interaction between a salt ion and its image charge. When combined with the Debye‐Hückel effect of salts on the solvation energy of protein charges (i.e., salting‐in), the characteristic curve of protein solubility versus salt concentration is obtained. The theory yields a direct link between the salting‐out effect and surface tension and is able to provide rationalizations for the effects of salt on the folding stability of several proteins. Proteins 2005. © 2005 Wiley‐Liss, Inc.
BAliBASE 3.0: Latest developments of the multiple sequence alignment benchmark
Authors: Thompson Julie D. , Koehl Patrice , Ripp Raymond , Poch Olivier
Published: July 2005

Multiple sequence alignment is one of the cornerstones of modern molecular biology. It is used to identify conserved motifs, to determine protein domains, in 2D/3D structure prediction by homology and in evolutionary studies. Recently, high‐throughput technologies such as genome sequencing and structural proteomics have lead to an explosion in the amount of sequence and structure information available. In response, several new multiple alignment methods have been developed that improve both the efficiency and the quality of protein alignments. Consequently, the benchmarks used to evaluate and compare these methods must also evolve. We present here the latest release of the most widely used multiple alignment benchmark, BAliBASE, which provides high quality, manually refined, reference alignments based on 3D structural superpositions. Version 3.0 of BAliBASE includes new, more challenging test cases, representing the real problems encountered when aligning large sets of complex sequences. Using a novel, semiautomatic update protocol, the number of protein families in the benchmark has been increased and representative test cases are now available that cover most of the protein fold space. The total number of proteins in BAliBASE has also been significantly increased from 1444 to 6255 sequences. In addition, full‐length sequences are now provided for all test cases, which represent difficult cases for both global and local alignment programs. Finally, the BAliBASE Web site (http://www‐bio3d‐igbmc.u‐strasbg.fr/balibase) has been completely redesigned to provide a more user‐friendly, interactive interface for the visualization of the BAliBASE reference alignments and the associated annotations. Proteins 2005. © 2005 Wiley‐Liss, Inc.
Different methylation characteristics of protein arginine methyltransferase 1 and 3 toward the Ewing Sarcoma protein and a peptide
Authors: Pahlich Steffen , Bschir Karim , Chiavi Claudio , Belyanskaya Larisa , Gehring Heinz
Published: July 2005

The multifunctional Ewing Sarcoma (EWS) protein, a member of a large family of RNA‐binding proteins, is extensively asymmetrically dimethylated at arginine residues within RGG consensus sequences. Using recombinant proteins we examined whether type I protein arginine methyltransferase (PRMT)1 or 3 is responsible for asymmetric dimethylations of the EWS protein. After in vitro methylation of the EWS protein by GST‐PRMT1, we identified 27 dimethylated arginine residues out of 30 potential methylation sites by mass spectrometry‐based techniques (MALDI‐TOF MS and MS/MS). Thus, PRMT1 recognizes most if not all methylation sites of the EWS protein. With GST‐PRMT3, however, only nine dimethylated arginines, located mainly in the C‐terminal region of EWS protein, could be assigned, indicating that structural determinants prevent complete methylation. In contrary to previous reports this study also revealed that trypsin is able to cleave after methylated arginines. Pull‐down experiments showed that endogenous EWS protein binds efficiently to GST‐PRMT1 but less to GST‐PRMT3, which is in accordance to the in vitro methylation results. Furthermore, methylation of a peptide containing different methylation sites revealed differences in the site selectivity as well as in the kinetic properties of GST‐PRMT1 and GST‐PRMT3. Kinetic differences due to an inhibition effect of the methylation inhibitor S‐adenosyl‐L‐homocysteine could be excluded by determining the corresponding Ki values of the two enzymes and the Kd values for the methyl donor S‐adenosyl‐L‐methionine. The study demonstrates the strength of MS‐based methods for a qualitative and quantitative analysis of enzymic arginine methylation, a posttranslational modification that becomes more and more the object of investigations. Proteins 2005. © 2005 Wiley‐Liss, Inc.
Mass spectrometric investigation of gaseous YbH, YbO and YbOH molecules
Authors: Brutti S. , Terai T. , Yamawaki M. , Yasumoto M. , Balducci G. , Gigli G. , Ciccioli A.
Published: July 2005

The high‐temperature gaseous molecules YbH, YbO and YbOH have been identified and their thermochemistry investigated by the Knudsen effusion mass spectrometry technique coupled with a controlled pressure gas inlet system. Solid ytterbium monosilicide and disilicide samples were made to react in the Knudsen cell with H2(g) and H2(g)/O2(g); in these conditions, several gaseous species (Yb, YbO, YbH, YbOH, SiO, SiO2, H2O) were formed under equilibrium conditions. The temperature dependences of the partial pressures of the observed gaseous molecules were analyzed to derive the YbX bond energies (X = H, O, OH). Selected values are D(YbH) = 179.4 ± 2.0 kJ mol−1, D(YbO) = 384 ± 10 mol−1 and D(YbOH) = 322 ± 12 kJ mol−1, and ΔatH(YbOH) = 746 ± 12 kJ mol−1. Density functional theory (DFT) calculations were also performed. Experimental and computational results are discussed and compared to previous data when available. The SiO/SiO2 high‐temperature gaseous equilibrium was also observed. Copyright © 2005 John Wiley & Sons, Ltd.
Analysis of vitamin E derivatives in serum using coordinated ion spray mass spectrometry
Authors: Al‐Talla Zeyad A. , Tolley Luke T.
Published: July 2005

A method for the extraction and analysis of tocopherols from serum using coordinated ion spray (CIS) mass spectrometry was developed and tested. The tocopherols were extracted from serum and analyzed by direct infusion into the mass spectrometer, bypassing the need for a liquid chromatography step. CIS is a method for improving the ionization efficiency of non‐polar compounds by adding metal ions to the electrospray solvent. The non‐polar analytes appear as metal adducts in the resulting mass spectrum. Silver was used as the metal ion for the CIS, causing analyte masses to be increased by 107 and 109 Da from the two main silver isotopes. Vitamin E succinate was added to the samples before extraction and was used as an internal standard to compensate for any variations in the extraction efficiency or mass spectrometric response. α‐Tocopherol and an ether‐linked analogue known as α‐TEA were analyzed in concentrations from 1.25–40 µg/mL (1.9–60 pg consumed). The response curve was constructed by comparing the response of the analytes to the internal standard and gave linear results with r2 values greater than 0.98. This new method was shown to be sensitive, reproducible, fast and required very small amounts of analyte. Copyright © 2005 John Wiley & Sons, Ltd.
Characteristic pH and electrolyte concentration dependences of 2‐aminopyridine‐derivatized oligosaccharides (N‐glycans) in sonic‐spray ionization mass spectrometry
Authors: Deguchi Kisaburo , Takegawa Yasuhiro , Hirabayashi Atsumu , Nakagawa Hiroaki , Nishimura Shin‐Ichiro
Published: July 2005

The intensities of ion signals from neutral oligosaccharides (N‐glycans) derivatized with 2‐aminopyridine (PA) were analyzed by ion trap mass spectrometry with a sonic‐spray ionization (SSI) source, in both positive‐ and negative‐ion modes, while varying the pH and concentration of ammonium acetate buffer solution. Two characteristic results are reported and discussed. The first characteristic is the pH dependence of the ion intensities; on increasing the solution pH from 4.3 to 8.6, positive ion intensities increase and negative ion intensities decrease. The second characteristic concerns the dependence of ion intensities on electrolyte concentration; on increasing the electrolyte concentration, the SSI efficiency for the PA N‐glycans first increases and then decreases. Assuming that the SSI mechanism essentially conforms to the statistical charging model and the charge residue model, a new model that focuses a great deal of attention on the counter (electrolyte) ion distribution surrounding the solvated analyte (PA N‐glycan) is proposed, in particular to rationalize the characteristic pH dependence. Copyright © 2005 John Wiley & Sons, Ltd.
Application of electrospray ionization with Fourier transform ion cyclotron resonance mass spectrometry for structural screening of core oligosaccharides from lipopolysaccharides of the bacteria Proteus
Authors: Kondakova Anna N. , Vinogradov Evgeny V. , Knirel Yuriy A. , Lindner Buko
Published: July 2005

Electrospray ionization with Fourier transform ion cyclotron resonance mass spectrometry (ESI‐FTICRMS) was used for screening and structural elucidation of core oligosaccharides isolated from lipopolysaccharides of bacteria of the genus Proteus. Mass spectra allowed the determination of the molecular masses with high accuracy and the estimation of the chemical heterogeneity of the samples. They did not, however, provide sufficient information to identify structural details of the branched oligosaccharides. Therefore, various fragmentation techniques for determining such details were examined. Infrared multiphoton dissociation tandem mass spectrometry (IRMPD‐MS/MS) experiments in negative ion mode resulted in cleavage between the structurally conserved inner core region and the variable outer core region. Positive ion capillary skimmer dissociation mass spectra showed numerous fragment ion peaks, including those corresponding to the subsequent cleavage of the glycosidic linkages starting from the non‐reducing end of the oligosaccharide. Despite their complexity, these mass spectrometric studies allowed confirmation of previously determined Proteus lipopolysaccharide core structures, and identification of new related structures in other strains of these bacteria. Copyright © 2005 John Wiley & Sons, Ltd.
A rapid sample preparation method for mass spectrometric characterization of N‐linked glycans
Authors: Yu Ying Qing , Gilar Martin , Kaska Jennifer , Gebler John C.
Published: July 2005

A rapid method for analysis of glycans of glycoproteins is presented. This method comprised deglycosylation, sample cleanup and matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) analysis of glycans. The enzymatic deglycosylation of N‐linked glycoproteins was enhanced in terms of speed and reproducibility using an enzyme‐friendly surfactant. The released glycans were desalted using a micro‐scale solid phase extraction (SPE) device packed with a hydrophilic interaction chromatography (HILIC) sorbent. Hydrophilic glycans were well retained by SPE, while salts and surfactants were removed from the sample. The glycans were eluted using 25–50 µL of solvent and analyzed directly without derivatization using MALDI‐MS. MALDI quadrupole time‐of‐flight (Q‐Tof) instrumentation was utilized for glycan profiling and structure characterization by tandem mass spectrometry (MS/MS). The presented method allows sensitive analysis of glycans benefiting from optimized deglycosylation reactions and efficient sample cleanup. Copyright © 2005 John Wiley & Sons, Ltd.
Ultrathin SiO2 on Si. VII. Angular accuracy in XPS and an accurate attenuation length
Authors: Seah M. P. , Spencer S. J.
Published: July 2005

Following an earlier study of the uncertainties for defining thicknesses by angle‐resolved XPS, one of the major instrumental uncertainties has been evaluated that limits both precision and accuracy. For analysis of the thicknesses of SiO2 on Si, certain angles of emission have been recommended, but an error of 1° in these angles leads directly to an error in the thickness of ∼1% from this contribution alone. This is significant since the total uncertainty required in the (International technology roadmap for semiconductors) ITRS is only 1%. In many instruments, to reduce sample‐stage vibration and for other reasons, the angle and other setting adjustments are engineered with backlash. This, combined with the manufacturer's tolerances, can lead to angular errors above 1°. We report here a device using a laser and reflectors, fixed to the sample mount, that allow the angle of emission to be set to a precision better than 0.1° and, furthermore, a method to set the zero angle of emission to 0.1°. Using this geometrical device as well as by measurements of intensities in XPS, it is deduced that the data in our earlier report for the CCQM (Consultative Committee for Amount of Substance) intercomparison were for angles 1.89° ± 0.15° too high. Consequently, by a re‐analysis of all of that data, we find that our recommended attenuation length data for the Si 2p photoelectrons in thermal SiO2 using Mg or Al Kα X‐rays should be increased to 2.996 nm and 3.485 nm, respectively, an increase of 1.2% on the originally calculated values. These values now have standard uncertainties of 0.54% instead of the 20% of the TPP‐2M calculations. This leads to an improved accuracy in the measurement of ultrathin thermal oxides on silicon by XPS, of better than 1% for thicknesses greater than 1.5 nm but less than 8 nm. © Crown copyright 2005. Reproduced with the permission of Her Majesty's Stationery Office. Published by John Wiley & Sons, Ltd.