bluuebunny/crossref_metadata_2025 huggingface dataset:
Meeting Special Needs: A Benefit That Adds Value for Both Employees and Employers
Authors: Vogel Nadine
Published: March 2006

For every 1,000 employees, approximately 90 to 150 are parents of children with special needs. These employees face many life challenges, including high out-of-pocket medical costs and intensive demands on their daily time and energy. This largely “hidden” employee demographic provides an opportunity for the human resources professional to broaden a company's benefits package in a way that is a win-win for both employees and employer. By tapping into a comprehensive program that provides no-cost workshops and individualized counseling programs, employers can meet the difficult needs of their workforce; decrease corporate liability; improve employee engagement, productivity and retention; and enhance their reputation as a preferred employer in the labor market. Employees benefit from accessing expertise that can help them plan for their children's future, especially in the area of establishing special-needs trusts that can protect their eligibility for government services long after their parents are gone.
A Marian Pilgrimage: Reflections and Questions about ARCIC's: Mary: Grace and Hope in Christ
Authors: Harris Harriet , Harris Alana
Published: March 2006

This article considers the recently released bilateral statement of the Anglican–Roman Catholic International Commission (ARCIC) on the role of Mary in the Church. As female commentators from the two communions, we explore the theology and methodology of the document, concentrating on the images it promotes of Mary and particular areas of contention for us, as feminist theologians. We contend that the Commission has not sufficiently acknowledged the problems that Mariology has, and can create, for women; nor the potential consequences of a re-reception of Marian devotion within our churches. However, we conclude by welcoming the call to pilgrimage contained in the Statement – to journey with and through Mary to a deepened faith and understanding of her son.
In vivo CD40 ligation can induce T cell-independent antitumor effects that involve macrophages
Authors: Lum Hillary D , Buhtoiarov Ilia N , Schmidt Brian E , Berke Gideon , Paulnock Donna M , Sondel Paul M , Rakhmilevich Alexander L
Published: March 2006

We have previously demonstrated T cell-independent antitumor and antimetastatic effects of CD40 ligation that involved natural killer (NK) cells. As CD40 molecules are expressed on the surface of macrophages (Mφ), we hypothesized that Mφ may also serve as antitumor effector cells when activated by CD40 ligation. Progression of subcutaneous NXS2 murine neuroblastomas was delayed significantly by agonistic CD40 monoclonal antibody (anti-CD40 mAb) therapy in immunocompetent A/J mice, as well as in T and B cell-deficient severe combined immunodeficiency (SCID) mice. Although NK cells can be activated by anti-CD40 mAb, anti-CD40 mAb treatment also induced a significant antitumor effect in SCID/beige mice in the absence of T and NK effector cells, even when noncytolytic NK cells and polymorphonuclear cells (PMN) were depleted. Furthermore, in vivo treatment with anti-CD40 mAb resulted in enhanced expression of cytokines and cell surface activation markers, as well as Mφ-mediated tumor inhibition in A/J mice, C57BL/6 mice, and SCID/beige mice, as measured in vitro. A role for Mφ was shown by reduction in the antitumor effect of anti-CD40 mAb when Mφ functions were inhibited in vivo by silica. In addition, activation of peritoneal Mφ by anti-CD40 mAb resulted in survival benefits in mice bearing intraperitoneal tumors. Taken together, our results show that anti-CD40 mAb immunotherapy of mice can inhibit tumor growth in the absence of T cells, NK cells, and PMN through the involvement of activated Mφ.
Wnt signaling regulates transendothelial migration of monocytes
Authors: Tickenbrock Lara , Schwäble Joachim , Strey Anke , Sargin Bülent , Hehn Sina , Baas Marion , Choudhary Chunaram , Gerke Volker , Berdel Wolfgang E , Müller-Tidow Carsten , Serve Hubert
Published: March 2006

The Wnt-signaling pathway plays a critical role in directing cell fate during embryogenesis. Several lines of evidence also suggest a role in inflammatory processes. Here, we analyzed whether Wnt signaling plays a role in leukocyte inflammatory responses. Monocytes from healthy donors expressed different Frizzled receptors, which are ligands for the Wnt molecules. Activation of the Wnt/β-catenin pathway by LiCl or Wnt3a increased β-catenin protein levels in monocytes but not in granulocytes. It is interesting that the activation of Wnt/β-catenin signaling via Wnt3a in monocytes resulted in a decrease in migration through an endothelial layer (human dermal microvascular endothelial cell-1). Further experiments revealed that the decrease in transendothelial migration was associated with specific monocyte adherence to endothelial cells after Wnt exposure. The specificity was verified by a lack of Wnt3a-induced adhesion to fibronectin, laminin, or collagen compared with endothelial interaction. Analysis of the distribution of β-catenin revealed a Wnt3a-induced increase of β-catenin in the cytoplasm. Wnt3a exposure did not result in any activation of the classical Wnt-target gene c-myc or a Wnt-target gene involved in cell adhesion (Connexin43). Our study implicates for the first time a role of canonical Wnt signaling in inflammatory processes in monocytes.
RGS1 and RGS13 mRNA silencing in a human B lymphoma line enhances responsiveness to chemoattractants and impairs desensitization
Authors: Han Jang-Il , Huang Ning-Na , Kim Dong-Uk , Kehrl John H
Published: March 2006

Chemokines bind receptors that are members of the G-protein-coupled receptor family. Chemokine receptors transduce intracellular signals by activating heterotrimeric G-proteins. Acting to limit and modulate heterotrimeric G-protein signaling is a family of proteins, termed regulator of G-protein signaling (RGS). Two of these proteins, RGS1 and RGS13, are well-expressed in germinal center B cells and many Burkitt’s lymphoma cell lines. Reducing RGS13 and to a lesser extent RGS1 expression in a Burkitt’s lymphoma cell line enhances responsiveness to two chemokines, CXC chemokine ligand 12 (CXCL12) and CXCL13, and reducing both mRNAs augments the responses more dramatically. The double knock-down (KD) cells respond better to restimulation with CXCL12 or CXCL13 after a primary stimulation with CXCL12 than do the control cells. The double-KD cells also exhibit a greater propensity to polarize and to develop multiple small lamellipodia. These results indicate that RGS1 and RGS13 act together to regulate chemokine receptor signaling in human germinal center B lymphocytes and provide evidence that they contribute significantly to the rapid desensitization of the signaling pathway.
Dependability of scores for a new ESL speaking assessment consisting of integrated and independent tasks
Authors: Lee Yong-Won
Published: March 2006

A multitask speaking measure consisting of both integrated and independent tasks is expected to be an important component of a new version of the TOEFL test. This study considered two critical issues concerning score dependability of the new speaking measure: How much would the score dependability be impacted by (1) combining scores on different task types into a composite score and (2) rating each task only once? To answer these questions, generalizability theory (G-theory) procedures were used to examine the impact of the numbers of tasks and raters per speech sample and of subsection lengths on the dependability of speaking scores. Univariate and multivariate G-theory analyses were conducted on rating data collected for 261 examinees for the study. The finding in the univariate analyses was that it would be more efficient to increase the number of tasks rather than the number of ratings per speech sample in maximizing the score dependability. The multivariate G-theory analyses also revealed that (1) the universe (or true) scores among the task-type subsections were very highly correlated and that (2) slightly larger gains in composite score reliability would result from increasing the number of listening - speaking tasks for the fixed section lengths.
Establishing test form and individual task comparability: a case study of a semi-direct speaking test
Authors: Weir Cyril J. , Wu Jessica R.W.
Published: March 2006

Examination boards are often criticized for their failure to provide evidence of comparability across forms, and few such studies are publicly available. This study aims to investigate the extent to which three forms of the General English Proficiency Test Intermediate Speaking Test (GEPTS-I) are parallel in terms of two types of validity evidence: parallel-forms reliability and content validity. The three trial test forms, each containing three different task types (read-aloud, answering questions and picture description), were administered to 120 intermediate-level EFL learners in Taiwan. The performance data from the different test forms were analysed using classical procedures and Multi-Faceted Rasch Measurement (MFRM). Various checklists were also employed to compare the tasks in different forms qualitatively in terms of content. The results showed that all three test forms were statistically parallel overall and Forms 2 and 3 could also be considered parallel at the individual task level. Moreover, sources of variation to account for the variable difficulty of tasks in Form 1 were identified by the checklists. Results of the study provide insights for further improvement in parallel-form reliability of the GEPTS-I at the task level and offer a set of methodological procedures for other exam boards to consider.
Multiple dichotomous-scored items in second language testing: investigating the multiple true-false item type under norm-referenced conditions
Authors: Dudley Albert
Published: March 2006

This study examined the multiple true-false (MTF) test format in second language testing by comparing multiple-choice (MCQ) and multiple true-false (MTF) test formats in two language areas of general English: vocabulary and reading. Two counter-balanced experimental designs - one for each language area - were examined in terms of the number of MCQ and MTF differentially responded to, MTF item dependency, reliability, and concurrent validity. The data were analysed by classical test theory (CTT) and Rasch analysis. The results showed a two- and three-fold increase in vocabulary and reading items answered, respectively. Participants responded to significantly more MTF items than MCQ, and further analysis revealed no item dependency for both language domains. Reliability increases were found in the reading tests. Item conversions did not alter the basic functioning of the MTF items, and common person equating plots demonstrated a steady relationship between MCQ and MTF person ability estimates.
Validation of a web-based test of ESL pragmalinguistics
Authors: Roever Carsten
Published: March 2006

Despite increasing interest in interlanguage pragmatics research, research on assessment of this crucial area of second language competence still lags behind assessment of other aspects of learners’ developing second language (L2) competence. This study describes the development and validation of a 36-item web-based test of ESL pragmalinguistics, measuring learners’ offline knowledge of implicatures and routines with multiple-choice questions, and their knowledge of speech acts with discourse completion tests. The test was delivered online to 267 ESL and EFL learners, ranging in proficiency from beginner to advanced. Evidence for construct validity was collected through correlational analyses and comparisons between groups. The effect of browser familiarity was found to be negligible, and learners generally performed as previous research would suggest: their knowledge of speech acts increased with proficiency, as did their knowledge of implicature. Their knowledge of routines, however, was strongly dependent on L2 exposure. Correlations between the sections and factor analysis confirmed that the routines, implicatures, and speech act sections are related but that each has some unique variance. The test was sufficiently reliable and practical, taking an hour to administer and little time to score. Limitations and future research directions are discussed.
Plasma markers of NO synthase activity in women after ovarian hyperstimulation: influence of estradiol on ADMA
Authors: Çevik Duygu , Unay Özlem , Durmusoglu Fatih , Yurdun Türkan , Bilsel A Serpil
Published: March 2006

The beneficial effects of estrogen on vasculature are partially explained by an estrogen-induced increase in nitric oxide (NO) synthesis. Asymmetric dimethylarginine (ADMA) is an endogenous competitive inhibitor of NO synthase. In the present study, the effect of 17β-estradiol (E2) on ADMA and NO synthesis was investigated both in vivo and in vitro. Plasma NO and ADMA levels were measured in healthy women at a low menstrual estrogenic stage (E2 < 100 pg/ml) and in women who were undergoing ovarian hyperstimulation (E2 > 2000 pg/ml) before in vitro fertilization embryo transfer. Primary human umbilical vein endothelial cell (HUVEC) cultures were incubated with and without 100 nM E2 for 24 hours and the NO and ADMA levels of the media were measured. A nitric oxide analyzer was used for the detection of NO metabolites. ADMA and L-arginine were measured by high-performance liquid chromatography after precolumn derivatization with o-phthaldialdehyde. The IVF patients with high plasma E2 concentrations had significantly lower (48%, n = 12) plasma ADMA and higher (56%, n = 14) NO levels than the women at a low estrogenic stage. The incubation of HUVEC cultures with estradiol resulted in a significant decrease (47%, n = 10) in ADMA and an increase (46%, n = 10) in NO concentration in the culture media. Estradiol, by reducing ADMA, may therefore facilitate NO synthesis in endothelial cells. The protective effects of estradiol on vasculature may partly be related to a reduction in ADMA levels.
Variability of flow-mediated dilation measurements with repetitive reactive hyperemia
Authors: Harris Ryan A , Padilla Jaume , Rink Lawrence D , Wallace Janet P
Published: March 2006

To capture the response of an acute intervention, multiple post intervention measurements of flow-mediated dilation (FMD) must be performed. The effect of repetitive reactive hyperemia on endothelial function and the measurement of FMD are unknown. The purpose of this investigation was (1) to examine the effect of repetitive reactive hyperemia on brachial artery FMD and (2) to determine whether brachial artery FMD is stable during a 2-h morning period. We investigated FMD in 20 apparently healthy college students on three randomized treatment days every 30 min (T30), 60 min (T60), and 120 min (T120) throughout a 2-h morning period (08.00 h to 10.00 h). An ANOVA ( p > 0.05) and ICC (>0.40) were both needed to confirm no difference among repetitive reactive hyperemia treatments. In response to repetitive reactive hyperemia, there was no difference ( p = 0.307; ICC > 0.40) within the first and last FMD measurements of each treatment condition or between treatment conditions ( p = 0.344; ICC > 0.40). FMD was similar ( p = 0.348) throughout the 2-h morning period. In conclusion, repetitive reactive hyperemia over a 2-h period has no effect on FMD measurements in apparently healthy college students. In addition, this study found no time trends for FMD measurements during the 2-h morning period to allow for pre/post intervention FMD measurements.
Cellular adhesion molecules and peripheral arterial disease
Authors: Brevetti Gregorio , Schiano Vittorio , Chiariello Massimo
Published: March 2006

Cellular adhesion molecules (CAMs), by mediating the recruitment of circulating leukocytes to the blood vessel wall and their subsequent migration into the subendothelial spaces, play a crucial role in all stages of atherosclerosis. Soluble forms of CAMs, probably derived from proteolytic shedding, are present in the circulation and their blood levels parallel the amount expressed on the cell surface. In patients with peripheral arterial disease (PAD), increased levels of soluble CAMs have been found during exercise-induced claudication, are associated with the presence, the severity and the extent of atherosclerosis in the arteries of the lower limbs, and portend a worse outcome. These findings have provided new insights into the pathophysiology of PAD and its consequences. However, further large population studies are needed to firmly establish whether increased levels of circulating CAMs give additive information to current risk assessment approaches, and to verify whether PAD patients with elevated levels of circulating CAMs would benefit from any specific therapy.
An unusual case of toe ulceration
Authors: Lankipalli Ramarao , Konkle Barbara , Mohler Emile R
Published: March 2006

We describe an unusual presentation of toe ulceration in a 39-year-old otherwise healthy man. The left fifth toe was painful for several months with ulceration at the tip. The other toes appeared cyanotic and discolored. Foot pulses were normal. Laboratory testing revealed the platelet count at 1208 thousand/microliter, with hemoglobin 19.2 g/dl and hematocrit 57%. The erythropoietin level was found to be markedly decreased at 1 mU/ml. The patient was given the diagnosis of polycythemia vera with iron deficiency. Phlebotomy was performed and aspirin and cytoreductive therapy with hydroxyurea was prescribed with resolution of the toe ulceration.
Masterclass series in peripheral arterial disease
Authors: Hiatt William R , Krantz Mori J
Published: March 2006

Peripheral arterial disease (PAD) of the lower extremities is a common and potentially life-threatening manifestation of systemic atherosclerosis. Significant PAD is identified by an ankle brachial index (ABI) <0.90; its presence is strongly associated with the major modifiable cardiac risk factors. Early detection and treatment of asymptomatic PAD is a current focus of numerous cardiovascular guideline organizations as less than a third of patients report typical claudication symptoms. This has created an ever-increasing treatment gap, whereby millions of eligible patients are inadequately treated. Risk factor management including exercise, smoking cessation, and aggressive treatment of lipids and blood pressure are essential in PAD patients. However, life-long antiplatelet therapy provides additional reductions in vascular events beyond aggressive risk factor management. The use of aspirin as well as more potent antiplatelet therapies such as thienopyridines holds promise for reducing atherothrombosis in this very high-risk population.
Does the association between serum endostatin, an endogenous anti-angiogenic protein, and acute myocardial infarction differ by race?
Authors: Iribarren Carlos , Herrinton Lisa J , Darbinian Jeanne A , Tamarkin Lawrence , Malinowski Donald , Vogelman Joseph H , Orentreich Norman , Baer David
Published: March 2006

Endostatin, an endogenous anti-angiogenic protein, has been linked to reduced atherosclerosis in animal models. We conducted a nested case-control study to ascertain whether decreased circulating endostatin might be associated with increased odds of acute myocardial infarction (AMI) and whether this association varied by sex or race. Cases were 211 subjects who subsequently developed AMI, and controls were 173 subjects free of cardiovascular disease matched on age, sex, race and follow-up time. In conditional logistic regression adjusting for traditional risk factors, the odds ratio of AMI per 1 SD increment in endostatin was 0.85 (95% confidence interval, 0.73-1.00). This association varied by race (but not by sex) such that a statistically significant inverse relation was found among Asians and white individuals and a significant positive relation among black individuals. Further research is needed to replicate these findings and to elucidate potential mechanisms for these race/ethnic differences.
Markers of vascular inflammation are associated with the extent of atherosclerosis assessed as angiographic score and treadmill walking distances in patients with peripheral arterial occlusive disease
Authors: Nylænde M , Kroese A , Stranden E , Morken B , Sandbæk G , Lindahl AK , Arnesen H , Seljeflot I
Published: March 2006

The importance of inflammation in atherosclerosis is well established in cardiovascular disease. However, limited data exist on the relationship between vascular inflammation and the severity of peripheral arterial occlusive disease (PAD). We investigated the relationship between biochemical markers of vascular inflammation and the diagnostic measures of PAD: ankle-brachial pressure index (ABI), maximum treadmill walking distance and angiographic score. In 127 patients (mean age 66 years; 64% males) with angiographically verified PAD, fasting blood samples were drawn for determination of selected soluble cell adhesion molecules, cytokines and chemokines. Tumor necrosis factor-α (TNFα), interleukin-6 (IL-6), monocyte chemoattractant protein-1 (MCP-1) and CD40 ligand (CD40L) were all significantly correlated with the angiographic score ( p < 0.05 for all). After adjustment for relevant co-variates, MCP-1 and CD40L remained statistically significant ( p < 0.01 for both). IL-6 was, independent of other risk factors, inversely correlated with the maximum treadmill walking distance ( p < 0.01). Our cross-sectional study in PAD patients showed that the vascular inflammatory markers MCP-1, CD40L and IL-6 were significantly associated with the extent of atherosclerosis, assessed by angiographic score and maximum treadmill walking distance. These findings indicate that vascular inflammation is implicated in PAD, which might be of importance in future diagnosis and treatment of the disease.
Limitation of the resting ankle-brachial index in symptomatic patients with peripheral arterial disease
Authors: Stein Russell , Hriljac Ingrid , Halperin Jonathan L , Gustavson Susan M , Teodorescu Victoria , Olin Jeffrey W
Published: March 2006

Peripheral arterial disease (PAD) has been demonstrated to be prevalent in the primary care setting. However, it has also been shown to be unrecognized and under-treated. Owing to the association with cardiovascular disease it has been recommended to screen high-risk patients for PAD in the primary care setting using the ankle-brachial index (ABI). ABI has been demonstrated to be highly sensitive and specific in diagnosing PAD in patients with significant stenosis. However, the utility in patients with less severe stenosis and calcified vessels is in question. The aims of this study were to determine the diagnostic utility of measuring the ABI at rest in patients referred to the vascular laboratory for evaluation of suspected PAD, and to assess the added value of pulse volume recordings and post-exercise studies in patients with a normal ABI. A computerized vascular diagnostic laboratory database was queried for symptomatic outpatients referred for measurement of segmental blood pressure, the ABI or pulse volume recordings by physicians not specialized in the evaluation and management of patients with peripheral vascular disease. Of 707 patients undergoing outpatient physiologic arterial evaluations between February 1, 2003 and July 31, 2004, 396 met these inclusion criteria. Data recorded included resting ABI, ABI following treadmill exercise test and the presence of abnormal pulse volume recordings. The study population ( n = 396) consisted of equal numbers of men and women (mean age 69 years, range 19-100 years). Among 396 studies, resting ABI values were normal in 183 (46.2%) and abnormal in 159 (40.2%). Of the 138 patients who underwent exercise testing, 84 had normal ABI readings at rest. In the 84 patients who had a normal ABI at rest and underwent exercise testing, the ABI fell below 0.9 after exercise in 26 (31%). Arterial non-compressibility was detected in 54 (13.6%) patients, whose average age was 67 years. Thirteen (24%) of those with non-compressible vessels had abnormal pulse volume recording (PVR) results, compared to five with normal resting ABI who had abnormal PVR findings (2.7%). In conclusion, this study demonstrated that nearly half of patients referred to the outpatient vascular laboratory because of suspected arterial disease had a normal resting ABI. While it is recommended that the ABI be measured at rest in patients at risk of PAD in primary care practice, these findings suggest that patients with symptoms of PAD should be more completely evaluated in a vascular laboratory. Furthermore, when the ABI is normal at rest in patients with symptoms of intermittent claudication, exercise testing is recommended to enhance the sensitivity for detection of PAD.
New Method for Preparation of Poly(phenylene-vinylene) Film
Authors: Iwatsuki Shouji , Kubo Masataka , Kumeuchi Toshiyuki
Published: March 2006

Poly(phenylene-chloroethylene) film was prepared by the vapor deposition polymerization of 1,9-dichloro[2.2]paracyclophane and was converted into fully extended π-conjugated poly (phenylene-vinylene) by thermal dehydrochlorination at 300 °C under nitrogen for 1 h.
Cu(II) Complexes of Glutathione. Coordination Mode, Spectroscopic Properties, and Lability
Authors: Hanaki Akira , Yokoi Hiroshi
Published: March 2006

Cu(II)-peptides were shown to coordinate to glutathione yielding transient ternary complexes as studied by both absorption and ESR spectrometries. Measurements were done by stopped-flow techniques. The ternary complexes in which glutathione functioned as a monodentate thiol ligand were stabilized significantly by ligation of an imidazole nitrogen to the metal ion.
Unusual Effects of Acetate Ion on Photosensitized Oxygenation of Naphthalene Derivatives via Electron Transfer
Authors: Yamashita Toshiaki , Tsurusako Taiji , Yasuda Masahide , Shima Kensuke
Published: March 2006

The oxygenation of 2-methylnaphthalene photosensitized by 9,10-dicyanoanthracene in an O2-saturated acetonitrile gave phthalic acid and 4-methylphthalic acid in the presence of Et4NOAc or KOAc/18-crown-6, but different products in the presence of Et4NBF4 and KClO4 and without a salt. The photosensitized ring oxygenation also occurred with naphthalene and 2,3-dimethylnaphthalene.
Aerobic Oxygenation of Olefinic Compounds into the Corresponding α-Hydroxy Ketones Using the Catalyst System of OsO4 and Ni(II) Complex
Authors: Takai Toshihiro , Yamada Tohru , Mukaiyama Teruaki
Published: March 2006

In the presence of the catalyst system of OsO4 and bis(3-methyl-2,4-pentanedionato)nickel(II), various olefinic compounds are directly converted into the corresponding α-hydroxy ketones in good yields with molecular oxygen and an aldehyde.
Detection and Quantification of CO Gas Based on the Dynamic Response of a Ceramic Sensor
Authors: Nakata Satoshi , Kaneda Yoshiaki , Nakamura Hiroko , Yoshikawa Kenichi
Published: March 2006

A novel method of gas-sensing is proposed based on the information of nonlinear, dynamic response of a ceramic gas sensor. A sinusoidal voltage is applied to a heater equipped with a SnO2 gas sensor and the resulting output resistance is analyzed by the Fast Fourier Transformation (FFT). It was found that the intensities of the higher harmonics exhibit characteristic changes with respect to different kind of gas.
Alkylation of Aromatic Heterocycles with Oxalic Acid Monoalkyl Esters in the Presence of Trivalent Iodine Compounds
Authors: Togo Hideo , Aoki Masahiko , Yokoyama Masataka
Published: March 2006

Aromatic heterocycles containing nitrogen atoms were easily alkylated with the half esters of oxalic acid, which were prepared from alcohols, in the presence of [bis(trifluoroacetoxy)iodo]benzene via radical decarboxylative pathways. This is the first method for the alkylation of aromatic heterocycles with alcohols via the formation of half esters of oxalic acid.
X-Ray Crystal Structure of p-lsopropyldihomooxacalix[4]arene-o-Xylene (1:1) Complex
Authors: Suzuki Kenji , Armah Anthony E , Fujii Satoshi , Tomita Ken-ichi , Asfari Zouhair , Vicens Jacques
Published: March 2006

The Crystal Structure of p-lsopropyldihomooxacalix[4]arene-o-Xylene Complexcomplex was determined by X-ray diffraction method. This oxacalixarene adopts a cone conformation involving o-xylene as a guest molecule.
Formation of Phenoxy Radical by Binuclear Iron(III) Complex and Hydrogen Peroxide System
Authors: Nishida Yuzo , Akamatsu Tetsuya , Nasu Miyuki
Published: March 2006

We have found that several peroxide adducts of binuclear iron(III) compounds react with phenols to yield a phenoxy radical, and concluded that the formation of the radical may be attributed to hydrogen atom abstraction by the peroxide adduct with electrophi1ic nature.
Automatic Doping of Polyaniline with Organic Electron Acceptors
Authors: Ohsawa Toshiyuki , Nishihara Hiroshi , Aramaki Kunitsugu , Yoshino Katsumi
Published: March 2006

Complexes of polyaniline (PANI) with various organic π-electron acceptors such as benzoquinones were prepared by the automatic doping method. Relation of their electrical, electrochemical and spectroscopic properties to the strength in electron affinity of the acceptors were revealed.
Regiochemistry of Boron Trifluoride Mediated Hydrolysis of Glycidyl Benzoates
Authors: Yoshitake Makoto , Kobayashi Hiroyuki , Yamamoto Makoto , Kohmoto Shigeo , Yamada Kazutoshi
Published: March 2006

Hydrolysis of glycidyl benzoates in the presence of BF3·OEt2 in CH2Cl2 affords regioisomeric triol mono benzoates, their ratios remarkably change depending on the temperature particularly in the reaction of 3,3-dimethylglycidyl benzoate.
Spin State and Rotational Orientation of Iron Porphyrin Complexes with Hindered 2-Methylbenzimidazole as Axial Ligands
Authors: Nakamura Mikio , Nakamura Nobuo
Published: March 2006

Sterically very hindered 2-methylbenzimidazole can bind high spin meso-tetraarylporphinatoiron(III) chloride to form a bis-ligated complex if the meso-aryl groups carry alkyl groups at 2,6-positions. The spin state and ligand orientation of this complex are discussed based on the NMR and EPR spectra.
New Reduction Catalysis of Metalloporphyrins. Catalytic Reduction of Nitrobenzene to Aniline with Tetraphenylporphyrinato-iron(III) Chloride–NaBH4 System
Authors: Sakaki Shigeyoshi , Mitarai Shinji , Ohkubo Katsutoshi
Published: March 2006

The (TPP)FeCl–NaBH4 system performs remarkably efficient catalytic reduction of nitrobenzene to aniline. (TPP)Co and (TPP)MnCl also catalyze the reduction of p-chloronitrobenzene to p-chloroaniline, while their catalytic activities are much lower than that of (TPP)FeCl.
Organic Ferromagnetism and Antiferromagnetism of 4-Methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl and 4-Acryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl
Authors: Sugimoto Hiroyuki , Aota Hiroyuki , Harada Akira , Morishima Yotaro , Kamachi Mikiharu , Mori Wasuke , Kishita Michihiko , Ohmae Norihiro , Nakano Motohiro , Sorai Michio
Published: March 2006

The temperature dependence of the magnetic susceptibilities for 4-methacryloyloxy- and 4-acryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl (MOTMP and AOTMP, respectively) was measured. Intermolecular magnetic coupling in these radicals was changed from antiferromagnetic to ferromagnetic by substituting hydrogen at α-position with a methyl group. A magnetic phase transition for MOTMP was observed at 0.14 K in the measurement of the temperature dependence of heat capacity. The circumstantial evidences support that the ordered state is of ferromagnet.
A Novel Laser-induced Synthesis of 1,1-Dichloroethylene from 1,1-Dichloroethane
Authors: Oshima Yoshito , Iguchi Kayoko , Tominaga Hiro-o , Koda Seiichiro
Published: March 2006

The laser-induced photochlorination of 1,1-dichloroethane followed by its dehydrochlorination has been examined in a flow reactor under normal pressure at 25–200 °C, which has been proved to be a novel direct synthesis of vinylidene chloride.
197Au Mössbauer Spectroscopic Study of the Ternary Systems (Ag,Au)2X (X = S and Se)
Authors: Sakai Hiroshi , Ando Manabu , Ichiba Sumio , Maeda Yutaka
Published: March 2006

197Au Mössbauer spectroscopy has been applied for the low-temperature β-phases of ternary systems, Ag2−xAuxX (X = S, and Se; x = 0.2 and 0.5). The nature of linear X–Au–X bonds present in these systems is discussed on the basis of the Mössbauer data and the bond distances.
Micellar Activation of Nucleophilic Cu2+-complexes of Surfactant Imidazole Ligands by Co-surfactants for the Hydrolysis of p-Nitrophenyl Picolinate. Importance of the Charge Site on Surfactant Ligand
Authors: Ogino Kenji , Yoshida Toshiharu , Nishi Kazuyoshi , Fujita Tsunehisa , Tagaki Waichiro
Published: March 2006

The micellar activation of the nucleophilic Cu2+-complexes of four surfactant imidazole ligands has been examined for the hydrolysis of p-nitrophenyl picolinate. A dramatic difference in the effect of co-surfactant was observed between the ligands having a charged group at the polar terminal and those having it at the inner site apart from the imidazole head group.
Chemistry of Benzopentathiepin. Formation of 2-Imino-1,3-benzodithioles from Alkyl or Aryl Isochalcogenocyanates with Benzopentathiepin
Authors: Sato Ryu , Yamaichi Shizuko
Published: March 2006

Various 2-imino-1,3-benzodithioles were synthesized in good yields by the reaction of alkyl or aryl isochalcogenocyanates, R–N=C=X (X = S or Se), with benzopentathiepin in the presence of triethylamine.
1H-NMR Spectroscopic Studies on the Ruthenocene and Its Salts
Authors: Watanabe Masanobu , Sano Hirotoshi
Published: March 2006

Temperature dependence of 1H-NMR spectra of a system containing ruthenocene and ruthenoceniumX+Y− salts (X; Cl, Br, I and Y; PF6, BF4, I3) in 1:1 molar ratio indicates the presence of intermolecular electron transfer between the ruthenocene and ruthenocenium species associated with an exchange of X atoms between the RuIICp2 molecules and RuIVCp2X+ cations.
New Lumazines from the Marine Polychaete, Odontosyllis undecimdonta
Authors: Inoue Shoji , Okada Kunisuke , Tanino Hideo , Kakoi Hisae , Ohnishi Yoshiko , Horii Naojiro
Published: March 2006

6-β-Methoxypropionyl-3-methyllumazine and 6-β-methoxypropionyl-1,3-dimethyllumazine, and 6-β-hydroxypropionyl-3-methyllumazine have been newly isolated from the swimming polychaete, Odontosyllis undecimdonta.
Intramolecular Hydrogen Migration of Geometrically Constrained 3,3-Diphenyl-2-t-butyloxaziridine
Authors: Kawamura Yasuhiko , Tsukayama Masao , Hayashi Shuzo , Horie Tokunaru
Published: March 2006

Thermolysis of 3,3-diphenyl-2-t-butyloxaziridine gave benzophenone oxime and isobutylene via the C–O bond fission followed by the intramolecular synchronous hydrogen migration from the t-butyl group without the intervention of the corresponding nitrone.
The Benzimidazole Dye Hoechst 8208 Intercalates into DNA
Authors: Kubota Yukio , Nakamura Hiroyuki
Published: March 2006

The interaction of the benzimidazole dye Hoechst 8208 (H8208) with DNA has been studied by optical, hydrodynamic, and 1H NMR techniques. All of the results clearly indicate that H8208 intercalates between successive DNA base pairs.
Heck-type Reaction of lodotrimethylsilane with Olefins Affording Alkenyltrimethylsilanes
Authors: Yamashita Hiroshi , Kobayashi Toshi-aki , Hayashi Teruyuki , Tanaka Masato
Published: March 2006

lodotrimethylsilane reacted with styrene derivatives in the presence of triethylamine and a palladium catalyst to give β-styrylsilanes.
Chlorination of Benzene with L-Zeolite Catalyst in the Presence of Oxygen and Various Solvents
Authors: Nakamura Tadashi , Shinoda Kiyonori , Yasuda Kensei
Published: March 2006

Benzene was chlorinated by using L type zeolite into p-dichlorobenzene (p-DCB) in a high yield in the presence of 1,2-dichloroethane (EDC) and oxygen.
Selective Adsorption of Palladium(II), Platinum(IV), and Mercury(II) on a New Chitosan Derivative Possessing Pyridyl Group
Authors: Baba Yoshinari , Hirakawa Hiroyuki
Published: March 2006

Crosslinked N-(2-pyridylmethyl)chitosan was newly synthesized by crosslinking N-(2-pyridylmethylidene)chitosan of the intermediate compound before reducing it so that the adsorptive activity is not lowered by the crosslinking. The pyridylmethylchitosan selectively adsorbed palladium(II), platinum(IV), and mercury(II) over base metals from hydrochloric acid.
Radical Anion of Nitrile Ylide by Dual Beam Irradiation of 3-(4-Biphenylyl)-2H-azirine at Low Temperature
Authors: Ishida Akito , Naito Ikuo , Takamuku Setsuo
Published: March 2006

Photolysis and the successive γ-radiolysis of 3-(4-biphenylyl)-2H-azirine at 77 K resulted in the formation of a novel intermediate with an absorption maximum at 425 nm, which was produced by one-electron reduction of the nitrile ylide. The intermediate was also produced by photochemical ring-opening of the azirine radical anion.
β-Selective Epoxidation of Cholesterol Derivatives with Molecular Oxygen and Aldehyde Catalyzed by Manganese(II) Complex
Authors: Yamada Tohru , Imagawa Kiyomi , Mukaiyama Teruaki
Published: March 2006

In the presence of a catalytic amount of bis(dipivaloylmethanato)manganese(II) (= Mn(dpm)2), various cholesterol derivatives are smoothly converted into the corresponding β-epoxides in good to high yields with combined use of molecular oxygen and isobutyraldehyde. These stereoselectivities are the reversal of the cases using peracid such as mCPBA.
Photochemical α-Cleavage Reaction of Levoglucosenone
Authors: Yamada Shinji , Matsumoto Masakatsu
Published: March 2006

Irradiation of levoglucosenone having a 6-membered cyclic α,β-unsaturated ketone structure with a high pressure mercury arc stereoselectively produced (Z)-β,γ-unsaturated acid derivatives. The mechanism of the formation of these products is explained in terms of the α-cleavage reaction which is scarcely observed in the photochemical reaction of α,β-unsaturated ketones.
Identification of Pyrolysis Reaction Model of Linear Low Density Polyethylene (LLDPE)
Authors: Kim Seungdo , Kavitha D
Published: March 2006

This paper described how to estimate the Arrhenius parameters as well as the pyrolysis reaction model of LLDPE from isothermal kinetic data. We used a custom-made thermobalance that is capable of monitoring a weight decrease with time under pure static condition and performed six isothermal kinetic experiments at 713, 718, 723, 728, 733, and 738 K that were chosen within a temperature range (710–740 K) where main decompositions were observed from non-isothermal kinetic results. Comparing experimental reduced-time-plots (RTPs) with theoretical ones, the pyrolysis reaction model of LLDPE is accounted for by “Avrami–Erofeev” model in the investigated temperature region, allowing its functional form to be 2(1 − α)[−ln(1 − α)]1/2. It is, hence, expected that the reaction order model adopted by the previous studies without verification is inappropriate to represent the pyrolysis reaction model of LLDPE. Bubble nucleation may be a major pyrolysis reaction mechanism of LLDPE. As heat is applied, the LLDPE is melted. Volatiles may be accumulated inside the melt until reaching a critical concentration where bubble nucleation sets forth. The rates of heat, mass, or momentum transfer in the LLDPE melt and its physico-chemical properties (especially viscosity) play an important role in characterizing the thermal decomposition kinetics of LLDPE.
Eulerian backtracking of atmospheric tracers. I: Adjoint derivation and parametrization of subgrid‐scale transport
Authors: Hourdin F. , Talagrand O.
Published: March 2006

The problem of identification of sources of atmospheric tracers is most classically addressed through either Lagrangian backtracking or adjoint integration. On the basis of physical considerations, the retro‐transport equation, which is at the basis of Lagrangian backtracking, can be derived in a Eulerian framework as well. Because of a fundamental time symmetry of fluid transport, Lagrangian or Eulerian backtracking can be used for inverting measurements of the concentration of an atmospheric tracer. The retro‐transport equation turns out to be the adjoint of the direct transport equation, with respect to the scalar product defined by integration with respect to air mass. In the present paper, the exact equivalence between the physically‐derived retro‐transport and adjoint equations is proved. The transformation from the direct to the retro‐transport equation requires only simple transformations. The sign of terms describing explicit advection is changed. Terms describing linear sources or sinks of tracers are kept unchanged. Terms representing diffusion by unresolved time‐symmetric motions of the transporting air are also unchanged. This is rigorously shown for turbulent eddy‐diffusion or mixing length theory. The case of subgrid‐scale vertical transport by non‐time‐symmetric motions of air is studied using the example of the Tiedtke mass‐flux scheme for cumulus convection. The retro‐transport equation is then obtained by simply inverting the roles of updraughts and downdraughts, as well as of entrainment and detrainment. Conservation of mass of the transporting air is critical for all those properties to hold. Copyright © 2006 Royal Meteorological Society
Eulerian backtracking of atmospheric tracers. II: Numerical aspects
Authors: Hourdin F. , Talagrand O. , Idelkadi A.
Published: March 2006

In Part I of this paper, a mathematical equivalence was established between Eulerian backtracking or retro‐ transport, on the one hand, and adjoint transport with respect to an air‐mass‐weighted scalar product, on the other. The time symmetry which lies at the basis of this mathematical equivalence can however be lost through discretization. That question is studied, and conditions are explicitly identified under which discretization schemes possess the property of time symmetry. Particular consideration is given to the case of the LMDZ model. The linear schemes used for turbulent diffusion and subgrid‐scale convection are symmetric. For the Van Leer advection scheme used in LMDZ, which is nonlinear, the question of time symmetry does not even make sense. Those facts are illustrated by numerical simulations performed in the conditions of the European Transport EXperiment (ETEX). For a model that is not time‐symmetric, the question arises as to whether it is preferable, in practical applications, to use the exact numerical adjoint, or the retro‐transport model. Numerical results obtained in the context of one‐dimensional advection show that the presence of slope limiters in the Van Leer advection scheme can produce in some circumstances unrealistic (in particular, negative) adjoint sensitivities. The retro‐transport equation, on the other hand, generally produces robust and realistic results, and always preserves the positivity of sensitivities. Retro‐transport may therefore be preferable in sensitivity computations, even in the context of variational assimilation. Copyright © 2006 Royal Meteorological Society
Diagnosis and tuning of observational error in a quasi‐operational data assimilation setting
Authors: Chapnik Bernard , Desroziers Gerald , Rabier Florence , Talagrand Olivier
Published: March 2006

Desroziers and Ivanov proposed a method to tune error variances used for data assimilation. The implementation of this algorithm implies the computation of the trace of certain matrices which are not explicitly known. A method proposed by Girard, allowing an approximate estimation of the traces without explicit knowledge of the matrices, was then used. This paper proposes a new implementation of the Desroziers and Ivanov algorithm, including a new computation scheme for the required traces. This method is compared to Girard's in two aspects: its use in the implementation of the tuning algorithm, and the computation of a quantification of the observation impacts on the analysis known as Degrees of Freedom for Signal. Those results are illustrated by studies utilizing the French data assimilation/numerical weather‐prediction system ARPEGE. The impact of a first quasi‐operational tuning of variances on forecasts is shown and discussed. Copyright © 2006 Royal Meteorological Society
Linear dynamics of non‐symmetric perturbations in geostrophic horizontal shear flows
Authors: Kalashnik M. V. , Mamatsashvili G. R. , Chagelishvili G.D. , Lominadze J. G.
Published: March 2006

The linear dynamics of non‐symmetric wave and vortex mode perturbations in spectrally stable geostrophic zonal flows with a constant horizontal shear along the meridional direction, when a fluid is incompressible and stratified, is investigated. Specific features of these dynamics are closely related to the non‐normality of the linear operators governing perturbation evolution in shear flows and are well interpreted in the framework of the non‐modal approach—by tracing the linear dynamics of spatial Fourier harmonics of perturbations in time. If the Rossby number Ro<1, there occurs an algebraic (asymptotically linear) amplification of non‐symmetric shear internal waves. It is shown that at Ro>1, in addition, there takes place an exponential/explosive transient growth of the waves that precedes the time interval of algebraic amplification. We also describe the evolution of pure vortex mode perturbations imposed initially on the mean flow. It is shown that at Ro∼1, pure vortex (aperiodic) perturbations are able to gain basic flow energy and then generate non‐symmetric shear internal waves. The studied linear phenomena are specific to geostrophic zonal flows and cast doubt on the filtering of fast wave perturbations in the traditional quasi‐geostrophic models of geophysical hydrodynamics. Copyright © 2006 Royal Meteorological Society
Sea‐breeze‐induced mass transport over complex terrain in south‐eastern France: A case‐study
Authors: Bastin S. , Drobinski P.
Published: March 2006

The structure and evolution of the sea breeze in southern France on 25 June 2001 is investigated experimentally and numerically. This study shows how interactions between the sea breeze, the synoptic flow and the complex terrain affect the sea‐breeze structure, and quantifies and discusses the air‐mass transport associated with the sea‐breeze circulation. The analysis of the front propagation and the associated turbulent kinetic energy budget allows four distinct stages of sea‐breeze front evolution to be identified. Quantification of the horizontal and vertical air‐mass fluxes is related to these four stages: the horizontal advection is directly linked to the intensity of the sea‐breeze flow. Two main mechanisms contribute to the vertical export within the free troposphere: anabatic upslope winds which are intensified by the sea‐breeze flow and frontogenesis at the sea‐breeze front which generates turbulence and mixing and upward motion. Copyright © 2006 Royal Meteorological Society