bluuebunny/crossref_metadata_2025 huggingface dataset:
Palladium-Catalyzed Reaction of Acyliron Complexes with Aryl Halides. A Convenient Synthesis of Aromatic Ketones
Authors: Koga Teruyoshi , Makinouchi Shinako , Okukado Nobuhisa
Published: July 2006

Acyliron complexes, easily prepared from disodium tetracarbonylferrate and alkyl halides, reacted with aryl iodides in the presence of a catalytic amount of Pd(PPh3)4 and a cocatalyst, ZnCl2, to give aromatic ketones in good yields. (R)-2-Methyl-1-phenyl-1-octanone was prepared starting from (S)-2-bromooctane in an excellent optical yield.
Synthesis of Poly(2,5-dimethoxy-p-phenylenevinylene) Film through a New Precursor Polymer
Authors: Momii Tatsuo , Tokito Shizuo , Tsutsui Tetsuo , Saito Shogo
Published: July 2006

Poly(2,5-dimethoxy-p-phenylenevinylene) was synthesized through a new precursor polymer. The new precursor polymer was soluble in organic solvents and chemically stable at room temperature.
A Facile Synthesis of (−)-β-Vetivone
Authors: Asaoka Morio , Takenouchi Kazuya , Takei Hisashi
Published: July 2006

A short step synthesis of the title compound from (R)-(−)-5-trimethylsilyl-2-cyclohexenone via stereoselective intramolecular alkylation is described.
Four New Metabolites Produced by Penicillium Citreo-viride B. on Addition of NaBr
Authors: Shizuri Yoshikazu , Shigemori Hideyuki , Sato Ryutaro , Yamamura Shosuke , Kawai Kazuaki , Furukawa Hideyuki
Published: July 2006

Four new metabolites (citreobiphenyl, precitreobiphenyl, citreoviranol, and demethylcitreoviranol) have been isolated from the mycelium of Penicillium citreo-viride B. (IFO 4692) incubated on the polished rice together with sodium bromide, and their structures have also been elucidated on the basis of their spectral data.
Isolation of the First Allylic Gold(III) Complex Having a Triphenylphosphine Ligand
Authors: Komiya Sanshiro , Ozaki Satoshi
Published: July 2006

A metathetical reaction of [cis
New Addition Reaction of Active Ester or Cyclic Ester with Epoxy Compounds Catalyzed by Insoluble Polystyrene-bound Quaternary Phosphonium or Ammonium Salts
Authors: Nishikubo Tadatomi , Shiina Atsushi , Isobe Naoki
Published: July 2006

Regioselective addition reaction of active ester S-phenyl thioacetate with 2-phenoxymethyloxirane was catalyzed by insoluble polystyrene-bound quaternary phosphonium or ammonium salts and gave 1-phenoxy-3-thiophenoxy-2-propyl acetate. Five-membered cyclic carbonates were also synthesized by the reaction of cyclic ester β- butyrolactone with some epoxy compounds using the same polymeric catalysts.
Photochemical Image Storage in Polymer Liquid Crystals
Authors: Ikeda Tomiki , Horiuchi Shin , Karanjit Durga B , Kurihara Seiji , Tazuke Shigeo
Published: July 2006

Amplified optical image storage has been demonstrated in polymer liquid crystals (PLC). A small amount (< 5 mol%) of a low molecular weight mesogen with a photoresponsive moiety, 4-butyl-4′-methoxyazobenzene (BMAB), was doped in the films of polyacrylates with mesogenic side chain, poly(4′-methoxyphenyl-4-acryloyloxyalkoxybenzoate)(PAn), in which the alkyl spacer length (CH2)n was varied as n = 2, 3, 5, and 6. Photoirradiation of the PA3/BMAB film with a 366 nm light caused trans→cis isomerization of BMAB, which induced simultaneously the nematic (N)→isotropic phase transition of the PLC films. This photochemically induced phase transition was reversible and photoirradiation with a 525 nm light which induced cis→trans isomerization restored the system to the initial phase (N). The photo-induced phase transition was found to be strongly dependent on molecular weight of the host PLC and temperature.
Regioselective Nitration of Aromatic Hydrocarbons by Metallic Nitrates on the K10 Montmorillonite under Menke Conditions
Authors: Laszlo Pierre , Vandormael Joseph
Published: July 2006

Aromatic hydrocarbons are nitrated with good regioselectivities by clay-supported cupric nitrate in the presence of acetic anhydride. The procedure commends itself by its simplicity and gives useful yields (75–98%). In each case, the predominant product can be predicted by consideration of the Hückel HOMO for the aromatic ring.
An Efficient Synthesis of erythro-β-Hydroxy-l-histidine, the Pivotal Amino Acid of Bleomycin-Fe(II)–O2 Complex
Authors: Owa Takashi , Otsuka Masami , Ohno Masaji
Published: July 2006

erythro-β-Hydroxy-l-histidine is efficiently synthesized in organic solvents from the aldol reaction of (R)-3-bromoacetyl-4-isopropyl-1,3-oxazolidin-2-one and 1-triphenylmethylimidazole-4-carbaldehyde followed by SN2 reaction with LiN3 and hydrogenation.
Optical Resolution of Sulfoximines by Complex Formation with Optically Active 2,2′-Dihydroxy-1,1′-binaphthyl or 1,6-Di(o-chlorophenyl)-1,6-diphenylhexa-2,4-diyne-1,6-diol
Authors: Mori Koji , Toda Fumio
Published: July 2006

Some alkyl aryl and dialkyl sulfoximines were resolved efficiently by complex formation with optically active 2,2′-dihydroxy-1,1′-binaphthyl and 1,6-di(o-chlorophenyl)-1,6-diphenylhexa-2,4-diyne-1,6-diol, respectively.
In-Situ Scanning Tunneling Microscopy of Platinum Electrode in Sulfuric Acid
Authors: Itaya Kingo , Higaki Katsutoshi , Sugawara Shizuo
Published: July 2006

An in-situ scanning tunneling microscope (STM) was applied to clean Pt surfaces in aqueous sulfuric acid solutions. An electrochemical pretreatment was employed for a Pt electrode. It was suggested that the migration of ad-atoms of Pt produced by the oxidation and reduction cycles should occur towards a particular crystallographic direction.
Structure and Receptor Participation of Periplanone A, the Sex Pheromone of the American Cockroach
Authors: Nishino Chikao , Kobayashi Koji , Fukushima Masako , Imanari Mamoru , Nojima Kazutetsu , Kohno Shizue
Published: July 2006

Periplanones A (24 μg) and B (15 μg), the sex pheromones of the American cockroach, were isolated from the materials derived from 11500 females. The structure of periplanone A was elucidated to be (1Z,5E,7S*,10R*)-10(14)-epoxy-1,4(15),5-germacratrien-9-one. Either pheromone was revealed to participate with the corresponding sex pheromone receptor.
Synthesis and Chiral Recognition Property of 3-Acetylamino-3-deoxy-β-cyclodextrin
Authors: Murakami Teiichi , Harata Kazuaki , Morimoto Satoshi
Published: July 2006

Mono( 3-acetylamino-3-deoxy)-β-cyclodextrin (4) was firstly prepared via regioselective ring opening of manno-epoxide by ammonia. 1H-NMR investigation clearly demonstrated that 4 recognized the chirality of mandelic acids and N-acetyl-phenylglycine by the formation of diastereomeric inclusion complexes.
Valence States of Layered Vanadium Chalcogenophosphates, VPS3 and V0.78PS3
Authors: Ichimura Kenji , Sano Mizuka
Published: July 2006

VPS3 and V0.78PS3 have been synthesized by calcination of elementary mixtures prepared in the ratios of V:P:S = 1:1:3 and 0.78:1:3, respectively. Their X-ray diffraction patterns indicate that they have the same crystalline structure and orientation of crystal growth. The X-ray photoelectron spectra of V2p show that the vanadium in V0.78PS3 is in a mixed valence state and the compound is expressed by the formula of (V0.32+V0.73+)0.78PS3.
Hydrocarbons in the Yamato-791198 Carbonaceous Chondrite from Antarctica
Authors: Naraoka Hiroshi , Shimoyama Akira , Komiya Masatoshi , Yamamoto Hiroshi , Harada Kaoru
Published: July 2006

Yamato-791198 yielded up to 44 aromatic hydrocarbons and related compounds in the range of naphthalene and pyrene, including almost all structural isomers of methyl- and dimethyl-naphthalene. Several predominant compounds were present at the level of 10−7 g/g. Normal alkanes(C12−C22) were predominant in the aliphatic hydrocarbons and were at the level of 10−8 g/g.
Alumina-anchored Cobalt(II) Schiff Base Catalyst for the Isomerization of Trimethyldicyanoquadricyclane to the Norbornadiene
Authors: Miki Sadao , Maruyama Toshiro , Ohno Toshinobu , Tohma Toshihiko , Toyama Shin-ichi , Yoshida Zen-ichi
Published: July 2006

N,N′-Disalicylidene-4-carboxy-1,2-phenylenediiminatocobalt(II) supported on polyaminesulfone modified alumina beads has been prepared. The immobilized complex revealed efficient catalysis for the conversion of trimethyldicyanoquadricyclane (TMDC-Q) to the corresponding norbornadiene (TMDC-NBD). Using a bench-scale fixed bed reactor, TMDC-Q in chlorobenzene (1 mol dm−3) isomerized to TMDC-NBD quantitatively during the flow through catalyst bed of only 20 cm with the temperature increase from 24.5 °C to 75 °C.
Lithium-ion Insertion/Extraction Reaction with λ-MnO2 in the Aqueous Phase
Authors: Ooi Kenta , Miyai Yoshitaka , Katoh Shunsaku , Maeda Hiroshi , Abe Mitsuo
Published: July 2006

The topotactic insertion of Li+ in λ-MnO2 involved an evolution of oxygen and a reduction of Mn(lV) to Mn(III) in a (LiCl + LiOH) solution. The major reaction could be represented as λ-MnO2 + xLiOH → LixMnO2 + (x/2)H2O + (x/4)O2, where x denotes moles of inserted Li+ per mole of λ-MnO2. The extraction of the inserted Li+ was studied by using a solution containing either an acid(HCl) or an oxidizing agent(Br2, K2S2O8).
Cellular Prion Protein in the Bovine Mammary Gland Is Selectively Expressed in Active Lactocytes
Authors: Didier Andrea , Dietrich Richard , Steffl Martin , Gareis Manfred , Groschup Martin H. , Müller-Hellwig Simone , Märtlbauer Erwin , Amselgruber Werner M.
Published: July 2006

The cellular prion protein (PrPc) is a highly conserved glycoprotein with a still enigmatic physiological function. It is mainly expressed in the central nervous system but accumulating data suggest that PrPc is also found in a broad spectrum of non-neuronal tissue. Here we investigated the cell-type-related PrPc expression in the bovine mammary gland by using immunohistochemistry (IHC), ELISA, Western blot, and real-time RT-PCR. Specific immunostaining of serial sections revealed that PrPc is selectively localized in mammary gland epithelial cells. Particularly strong expression was found at the basolateral surface of those cells showing active secretion. Results obtained by RT-PCR and ELISA complemented IHC findings. No correlation was found between the level of PrPc expression and other parameters such as age of the animals under study or stage of lactation.
Preliminary Comparison of Quantity, Quality, and Microarray Performance of RNA Extracted From Formalin-fixed, Paraffin-embedded, and Unfixed Frozen Tissue Samples
Authors: Scicchitano Marshall S. , Dalmas Deidre A. , Bertiaux Melissa A. , Anderson Shawn M. , Turner Leah R. , Thomas Roberta A. , Mirable Rossana , Boyce Rogely W.
Published: July 2006

Microarrays have been used to simultaneously monitor the expression of thousands of genes from biological samples, an approach that can potentially uncover previously unrecognized functions of genes. Microarray analyses can rarely be conducted retrospectively because of the requirement for RNA to be obtained from fresh or unfixed frozen tissues. Archived pathology specimens would need to be used for retrospective analyses, and these are typically preserved as formalin-fixed, paraffin-embedded (FFPE) tissue. Formalin-fixed tissues have been shown to yield compromised RNA compared with that obtained from frozen tissue. To begin to assess the performance of RNA extracted from FFPE samples on a microarray format, we compared RNA from a model system of pelleted lipopolysaccharidestimulated human bone marrow stromal cells that were snap frozen with RNA from FFPE cells. RNA integrity and Affymetrix quality control parameters were assessed, and differentially regulated genes were analyzed with Ingenuity Pathway Analysis software. Results demonstrate that both snap-frozen and FFPE samples yielded intact RNA suitable for amplification prior to Affymetrix GeneChip analysis. Although some transcriptional information was lost with RNA extracted from the FFPE samples, Ingenuity Pathway Analysis revealed that the major pathways identified as affected by drug treatment were similar. Results show that FFPE samples are amenable to Affymetrix GeneChip analysis, expanding the possibility for expression profiling on archived tissue blocks in pathology laboratories. (J Histochem Cytochem 54:1229-1237, 2006)
Maternal testosterone levels during pregnancy are associated with offspring size at birth
Authors: Carlsen S M , Jacobsen G , Romundstad P
Published: July 2006

Objective: Animal studies have indicated that maternal androgen levels influence the intrauterine environment and development of the offspring. Human data are missing. We therefore investigated the possible association between maternal androgens and offspring size at birth in humans.

Design: A random sample of parous Caucasian women (n = 147) was followed prospectively through pregnancy.

Methods: Maternal serum levels of dehydroepiandrosterone sulfate (DHEAS), androstenedione, testosterone and sex hormone-binding globulin (SHBG) were measured at gestational weeks 17 and 33. The main outcome measures were weight and length at birth. Associations between maternal androgen levels and offspring birth weight and length were investigated using multiple linear regression modeling adjusted for potential confounding by maternal height, pre-pregnancy body mass index, smoking, parity, offspring gender and gestational age at birth.

Results: Elevated maternal testosterone levels at week 17 and 33 were both associated with lower birth weights and lengths. Accordingly, at week 17, an increase in maternal testosterone levels from the 25th to the 75th percentile was associated with a decrease in birth weight by 160 g (95% confidence interval (CI); 29–290 g), while at week 33 that estimate was 115 g (95% CI; 21–207 g). No similar associations were observed for DHEAS, androstenedione or SHBG.

Conclusions: Elevated maternal testosterone levels during human pregnancy are associated with growth restriction in utero. Our results support animal studies, which have indicated that maternal androgen levels influence intrauterine offspring environment and development.
Frequency of the metabolic syndrome in obese Spanish pediatric population
Authors: López-Capapé Marta , Alonso Milagros , Colino Esmeralda , Mustieles Carmen , Corbatón José , Barrio Raquel
Published: July 2006

Objective: Obesity is associated with insulin-resistance (IR), type 2 diabetes (T2D) and a constellation of cardiovascular risk factors at the early years of life. These features define the so-called metabolic syndrome (MS).

Aims: To assess the frequency of the MS among obese pediatric Spanish population and analyse the individual contribution and the predictive potential of individual components to the development of the syndrome.

Patients and methods: A total of 429 patients, 220 boys and 209 girls, aged 4–18 years, with a body mass index of > 2 standard deviation scores for Spanish normative charts, were included in the study. Forty-seven percent were prepubertal and ten percent had Hispanic ethnicity. HbA1c, lipids, liver enzymes and uric acid levels were determined from blood and a standard 2-h oral glucose tolerance test was performed. MS was defined by the National Cholesterol Education Program’s Adult Treatment Panel III criteria modified by Cook as having at least three features among: obesity, low high-density lipoprotein (HDL), hypertriglyceridemia, hypertension (HTA) or impaired glucose metabolism (IGM). We defined IR as homeostatic model assessment of IR index and/or fasting insulin levels> 95th centile of the control population.

Results: Almost 18% of the patients had MS, with significantly higher frequency in Hispanic (32%) than in Caucasian (16%) population. There were no differences by sex or pubertal status. Prevalence of low HDL, HTA, hypertriglyceridemia and IGM were 27, 23, 16 and 7% respectively. No silent T2D was identified. According to International Obesity Task Force charts, 22% of the patients were overweight and not obese, but no differences in the frequency of individual features of MS between these two groups were observed. Among IR patients (35% of our population), the frequency of MS reached 28%. IR predicted the presence of MS independently from age and race.

Conclusion: MS is present in 18% of our obese pediatric population. IR is closely associated with the components of MS and strongly predicts its development.
The Danish investigation on iodine intake and thyroid disease, DanThyr: status and perspectives
Authors: Laurberg Peter , Jørgensen Torben , Perrild Hans , Ovesen Lars , Knudsen Nils , Pedersen Inge Bülow , Rasmussen Lone B , Carlé Allan , Vejbjerg Pernille
Published: July 2006

Objective: Denmark was an area of iodine deficiency, and mandatory iodine fortification of table salt and salt in bread (13 p.p.m. iodine) was initiated in 2000/2001. The Danish investigation on iodine intake and thyroid disease (DanThyr) is the monitoring of the iodine fortification program.

Design and methods: DanThyr consists of three main parts: a study of population cohorts initialized before (n = 4649) and after (n = 3570) iodization of salt, a prospective identification of incident cases of overt hyper- and hypothyroidism in a population of around 550 000 people since 1997, and compilation of data from the national registers on the use of thyroid medication, thyroid surgery, and radioiodine therapy. Studies were carried-out in parallel in subcohorts living in areas with differences in iodine content of ground water.

Results: The study showed profound effects of even small differences in iodine intake level on the prevalence of goiter, nodules, and thyroid dysfunction. Mild and moderate iodine deficiency was associated with a decrease in serum TSH with age. Other environmental factors were also important for goiter development (increase in risk, smoking and pregnancy; decrease in risk, oral contraception and alcohol consumption), and the individual risk depended on the genetic background. Environmental factors had only a minor influence on the prevalence of thyroid autoantibodies in the population. There were more cases of overt hypothyroidism in mild than in moderate iodine deficiency caused by a 53% higher incidence of spontaneous (presumably autoimmune) hypothyroidism. On the other hand, there were 49% more cases of overt hyperthyroidism in the area with moderate iodine deficiency. The cautious iodine fortification program, aiming at an average increase in iodine intake of 50 μg/day has been associated with a 50% increase in incidence of hyperthyroidism in the area with the most severe iodine deficiency. The incidence is expected to decrease in the future, but there may be more cases of Graves’ hyperthyroidism in young people.

Conclusion: A number of environmental factors influence the epidemiology of thyroid disorders, and even relatively small abnormalities and differences in the level of iodine intake of a population have profound effects on the occurrence of thyroid abnormalities. Monitoring and adjustment of iodine intake in the population is an important part of preventive medicine.
Thigh intermuscular fat is inversely associated with spontaneous GH release in post-menopausal women with abdominal obesity
Authors: Franco Celina , Veldhuis Johannes D , Iranmanesh Ali , Brandberg John , Lönn Lars , Andersson Björn , Bengtsson Bengt-Åke , Svensson Johan , Johannsson Gudmundur
Published: July 2006

Context: The metabolic syndrome is characterized by an increased accumulation of visceral adipose tissue (VAT) and blunted GH secretion. There are, however, no data on the association between GH secretion and other fat depots (in liver and muscle).

Objective/design: The aim of this cross-sectional study, which included 20 post-menopausal women with abdominal obesity, was to determine the association between GH secretion and regional adipose tissue (AT) distribution. Twelve-hour GH profiles (2000–0800 h) were performed by blood sampling every 20 min. GH was analyzed using an ultra-sensitive assay followed by approximate entropy (ApEn) and deconvolution analysis.

Results: In simple regression analyses, both basal and pulsatile GH secretions correlated negatively with VAT and thigh intermuscular adipose tissue (IMAT), but not with hepatic fat content. There was no correlation between ApEn and the AT depots studied. In multiple regression analysis, pulsatile GH secretion correlated inversely with thigh IMAT (B-coefficient = −0.67; P < 0.01), whereas the correlation with VAT became non-significant. Furthermore, in multiple regression analysis, basal GH secretion correlated negatively with VAT (B-coefficient = −0.77; P = 0.001), but not significantly with thigh IMAT.

Conclusion: In post-menopausal women with abdominal obesity, pulsatile GH secretion demonstrated an independent, negative association with thigh IMAT, whereas basal GH secretion showed an independent, negative association with VAT. These findings suggest that the neuroendocrine association between fat mass and somatotropic axis is depot-dependent. We have identified thigh IMAT to be important in this interplay.
Validity and clinical applicability of the acromegaly quality of life questionnaire, AcroQoL: a 6-month prospective study
Authors: Webb Susan M , Badia Xavier , _ _
Published: July 2006

Objective: Validate the acromegaly quality of life (AcroQoL) questionnaire as a disease-generated questionnaire, which analyses physical and psychological domains, the latter subdivided into appearance and personal relationship sub-scales, to evaluate health-related quality of life (HRQoL) in acromegaly.

Design: Prospective, observational multicenter study.

Methods: One hundred and six patients with acromegaly, 42 with active disease studied basally and 6 months after treatment (‘sensitivity to change’ group), and 64 with treated, stable disease, studied twice within 1 month (‘reliability’ group) were included. As controls, a reference Spanish population (n = 12 245 for the EuroQoL questionnaire) and 157 obese patients (body mass index > 30 kg/m2) were studied basally. Socio-demographic data, clinical activity, co-morbidity, GH, IGF-I, and HRQoL (overall perception of health state, EuroQoL and AcroQoL in the obese controls and acromegalic patients) were evaluated.

Results: Globally, AcroQoL scored worse in the ‘sensitivity to change’ group than in the ‘reliability’ group (56 ± 20 vs 65 ± 18, P < 0.05), but did not discriminate between patients and obese controls. The psychological domain was worse in the ‘sensitivity to change’ group than obese controls (P < 0.05). Appearance was the most affected sub-scale in acromegaly and significantly worse than in obese controls. The sub-scale personal relationships of AcroQoL were less affected in the ‘reliability’ group than in obese controls (P < 0.05). Patients with acromegaly and obese controls showed more problems on the EuroQoL than general Spanish population. Significant correlations were observed globally and for each dimension between AcroQoL and the generic questionnaires. On re-testing, no change was observed in the ‘reliability’ group in any questionnaire, demonstrating good test–re-test reliability. In the ‘sensitivity to change’ group after 6 months of treatment, there was improvement in the generic questionnaires and in AcroQoL score (P < 0.01). Internal consistency of AcroQoL was good (Cronbach’s α > 0.7). No correlation between AcroQoL and GH or IGF-I was observed.

Conclusion: AcroQoL questionnaire is a valid tool for the assessment of HRQoL in clinical practice in patients with acromegaly.
Pregnancy in acromegaly: a one-center experience
Authors: Cozzi Renato , Attanasio Roberto , Barausse Michela
Published: July 2006

Objective and design: The aim of the study was the retrospective evaluation of pregnancy in acromegalic women attending our center.

Patients and methods: Six active acromegalic women (30–35-years old, disease duration 5–17 years) underwent seven pregnancies. Four patients had macroadenoma and two microadenoma; four had surgery; and two had been treated primarily with drugs. Before conception, GH and IGF-I were 5.4 ± 0.8 and 430 ± 58 μg/l respectively. GH (by an assay unable to distinguish pituitary hormone from placental variant), IGF-I, and prolactin (PRL) levels were assessed before conception, every 3 months, and after delivery; visual field and magnetic resonance imaging were performed before delivery in the only patient with macroadenoma not previously operated on and after delivery in all.

Results: All the women conceived normally, after discontinuation of medications in five cases and, while on treatment with depot somatostatin analogs in two (discontinued after confirmation of pregnancy). All patients remained off-treatment throughout pregnancy, had uneventful pregnancies, and term delivery. The babies were healthy and normal in length and weight. Breast-feeding was allowed in four cases. During pregnancy, GH levels showed variable changes; IGF-I, notwithstanding the withdrawal of any GH hypersecretion-suppressive treatment, remained close to normal limits in all subjects and returned to pathological levels after delivery; PRL increased physiologically, returning to baseline level after delivery. In one of the two patients primarily treated with drugs, GH levels increased and the tumor regrew throughout pregnancy, although without visual impairment.

Conclusions: Pregnancy in acromegalic women has a normal course leading to a normal delivery, and produces normal babies. GH levels show variable changes, but decrease in most patients. IGF-I levels remain normal without medical treatment.
Pierson Syndrome: A Novel Cause of Congenital Nephrotic Syndrome
Authors: VanDeVoorde Rene' , Witte David , Kogan Jillene , Goebel Jens
Published: July 2006

In this report, we describe a newborn infant who presented with congenital nephrotic syndrome and renal insufficiency, as well as bilateral microcoria. This constellation of findings is a hallmark of Pierson syndrome, a newly recognized genetic disorder that is caused by a deficiency of β2 laminin in the basement membrane. Our patient demonstrated classic histopathologic findings of Pierson syndrome on renal biopsy, including absence of β2 laminin on immunofluorescent staining, and genetic testing confirmed the diagnosis. We conclude that Pierson syndrome should be included in the differential diagnosis for congenital nephrotic syndrome, especially in patients with ocular abnormalities.
Prophylaxis Against Venous Thromboembolism in Acutely Ill Medical Patients: An Observational Study
Authors: Peterman Carla M. , Kolansky Daniel M. , Spinler Sarah A.
Published: July 2006

Study Objectives. To determine the risk factors for venous thromboembolism (VTE) and the rates of prophylactic measures used in acutely ill medical patients.

Design. Prospective observational study.

Setting. Academic tertiary care medical center.

Patients. One hundred seventy‐nine patients admitted to three general medical units over 30 consecutive days and hospitalized for at least 3 days.

Measurements and Main Results. On concurrent review of the patients' medical records, 138 (77.1%) of 179 patients received one or more forms of VTE prophylaxis during their hospital stay. Of 41 (22.9%) patients receiving no VTE prophylaxis, 22 (53.7%) had and 19 (46.3%, or 10.6% of the total population) did not have a documented contraindication to anticoagulation. One hundred ten patients (61.5%) had three or more documented VTE risk factors for VTE. The most common prophylaxis was unfractionated heparin 5000 U injected subcutaneously twice/day. Therapeutic anticoagulation was given to 51 patients (28.5%) at some time during their hospitalization for indications other than VTE treatment. Two developed symptomatic VTE (1.1%) while hospitalized. Four patients (2.2%) receiving anticoagulants had adverse outcomes. One patient had minor bleeding, and one developed heparin‐induced thrombocytopenia without thrombosis.

Conclusion. Rates of VTE prophylaxis were higher than previously reported rates, although no formalized guidelines, standardized order sets, alerting programs, training, or risk‐stratification tools were used during the study period. Rates of adverse events were low.
Long‐term Use of Atypical Antipsychotics in Bipolar Disorder
Authors: Ehret Megan J. , Levin Gary M.
Published: July 2006

Bipolar disorder is a chronic disease that may require lifetime treatment. The maintenance therapy of bipolar disorder can be challenging for the treating clinician. Currently, according to the American Psychiatric Association (APA) guidelines, lithium, valproic acid, lamotrigine, carbamazepine, oxcarbazepine, and the antipsychotics are recommended for the maintenance treatment of bipolar disorder. The antipsychotics are recommended to be continued only if the clinician decides that they are necessary for the control of persistent psychosis or for prophylaxis against recurrence. Although the APA guidelines provide sufficient evidence for the use of these mood stabilizers, newer drugs such as the atypical antipsychotics are being investigated for use in the maintenance phase of treatment of bipolar disorder.
Atypical Warfarin‐Induced Skin Necrosis
Authors: Ward Ceressa T. , Chavalitanonda Nann
Published: July 2006

Warfarin‐induced skin necrosis (WISN) is a disorder of unclear etiology that predominantly affects obese women. Although WISN typically occurs within the first 10 days of warfarin therapy, some patients develop the complication several years after warfarin exposure. We describe the case of a 43‐year‐old Caucasian woman with a history of recurrent thromboembolic disorders, protein S deficiency, and multiple exposures to warfarin who came to the emergency room with complaints of worsening dermatitis that had progressed over a 15‐hour period. Examination revealed multiple, diffuse “lace‐like” erythematous eruptions with superimposed lesions that were tender, ulcerated, and crusted. A biopsy was performed, and histopathologic findings were consistent with WISN. Based on the Naranjo adverse drug reaction probability scale, a probable causal relationship existed between warfarin and skin necrosis in this patient. Since treatment is generally supportive, prompt and prudent evaluation of suspicious skin lesions is necessary to prevent the serious sequelae associated with WISN.
Site of pheromone biosynthesis and isolation of HMG‐CoA reductase cDNA in the cotton boll weevil, Anthonomus grandis
Authors: Taban A. Huma , Fu Jessica , Blake Jacob , Awano Ami , Tittiger Claus , Blomquist Gary J.
Published: July 2006

Isolated gut tissue from male cotton boll weevil, Anthonomus grandis (Coleoptera: Curculionidae), incorporated radiolabeled acetate into components that co‐eluted with monoterpenoid pheromone components on HPLC. This demonstrates that pheromone components of male A. grandis are produced de novo and strongly suggests that pheromone biosynthesis occurs in gut tissue. A central enzyme in isoprenoid biosynthesis is 3‐hydroxy‐3‐methylglutaryl‐CoA reductase (HMG‐R), and a full‐length HMG‐R cDNA was isolated from A. grandis. The predicted translation product was 54 and 45% identical to HMG‐R from Ips paraconfusus and Drosophila melanogaster, respectively. HMG‐R gene expression gradually increased with age in male A. grandis, which correlates with pheromone production. However, topical application of JH III did not significantly increase HMG‐R mRNA levels. Arch. Insect Biochem. Physiol. 62:153–163, 2006. © 2006 Wiley‐Liss, Inc.
A randomized controlled trial with an anti‐CCL2 (anti–monocyte chemotactic protein 1) monoclonal antibody in patients with rheumatoid arthritis
Authors: Haringman Jasper J. , Gerlag Danielle M. , Smeets Tom J. M. , Baeten Dominique , van den Bosch Filip , Bresnihan Barry , Breedveld Ferdinand C. , Dinant Huib J. , Legay Francois , Gram Hermann , Loetscher Pius , Schmouder Robert , Woodworth Thasia , Tak Paul P.
Published: July 2006

Objective

Chemokines such as CCL2/monocyte chemotactic protein 1 (MCP‐1) play a key role in leukocyte migration and are potential targets in the treatment of chronic inflammatory disorders. The objective of this study was to evaluate the effects of human anti–CCL2/MCP‐1 monoclonal antibody (ABN912) treatment in patients with rheumatoid arthritis (RA).

Methods

Patients with active RA were enrolled in a randomized, placebo‐controlled, dose‐escalation study of ABN912. Infusions were administered on day 1 and day 15. In the dose‐escalation phase, 4 cohorts of 8 patients each underwent serial arthroscopic biopsy of synovial tissue. Immunohistochemistry and digital image analysis were used to characterize biomarkers in synovial tissue. Laboratory evaluation included pharmacokinetic analysis and immunotypic studies of peripheral blood mononuclear cells. To assess the clinical effects of treatment with ABN912, an additional 21 patients were treated with the highest dose tolerated.

Results

The total study population comprised 45 patients: 33 patients received ABN912, and 12 patients received placebo. ABN912 treatment was well tolerated. Unexpectedly, there was a dose‐related increase in ABN912‐complexed total CCL2/MCP‐1 levels in peripheral blood, up to 2,000‐fold. There was no detectable clinical benefit of ABN912 compared with placebo, nor did treatment with the study drug result in a significant change in the levels of biomarkers in synovial tissue and peripheral blood.

Conclusion

ABN912 treatment did not result in clinical or immunohistologic improvement and may have been associated with worsening of RA in patients treated with the highest dose. The results might be related to the greatly increased level of total CCL2/MCP‐1 in serum that was observed following treatment with ABN912. This observation may be relevant for a variety of antibody‐based therapies.
Proinflammatory high‐density lipoprotein as a biomarker for atherosclerosis in patients with systemic lupus erythematosus and rheumatoid arthritis
Authors: McMahon Maureen , Grossman Jennifer , FitzGerald John , Dahlin‐Lee Erika , Wallace Daniel J. , Thong Bernard Y. , Badsha Humeira , Kalunian Kenneth , Charles Christina , Navab Mohamad , Fogelman Alan M. , Hahn Bevra H.
Published: July 2006

Objective

Women with systemic lupus erythematosus (SLE) have a 7–50‐fold increased risk of coronary artery disease (CAD). In the general population, oxidized low‐density lipoprotein (ox‐LDL) increases the risk for CAD. Normal high‐density lipoproteins (HDLs) protect LDL from oxidation; proinflammatory HDLs do not. This study was undertaken to determine whether patients with SLE, who have chronic inflammation that causes oxidative damage, have more proinflammatory HDL and higher levels of ox‐LDL, thus predisposing them to atherosclerosis.

Methods

One hundred fifty‐four women with SLE, 48 women with rheumatoid arthritis (RA), and 72 healthy controls were studied. The ability of the patients' HDL to prevent oxidation of normal LDL was measured. Values >1.0 (the value assigned for LDL oxidation in the absence of HDL) after the addition of HDL indicated proinflammatory HDL. Plasma ox‐LDL levels were measured as the amount of oxidation produced by the patient's LDL after the removal of HDL.

Results

SLE patients had more proinflammatory HDL (mean ± SD score 1.02 ± 0.57, versus 0.68 ± 0.28 in controls [P < 0.0001] and 0.81 ± 0.22 in RA patients [P = 0.001 versus SLE patients]). A higher proportion of SLE patients had proinflammatory HDL: 44.7% of SLE patients versus 4.1% of controls and 20.1% of RA patients had scores >1.0 (P < 0.006 between all groups). Levels of ox‐LDL correlated with levels of proinflammatory HDL (r = 0.37, P < 0.001). SLE patients with CAD had significantly higher proinflammatory HDL scores than patients without CAD (P < 0.001).

Conclusion

HDLs are proinflammatory in a significant proportion of SLE patients and are associated with elevated levels of ox‐LDL. Abnormal HDLs impair the ability to prevent LDL oxidation and may predispose to atherosclerosis.
Increased arthritis susceptibility in cartilage proteoglycan–specific T cell receptor–transgenic mice
Authors: Berlo Suzanne E. , Guichelaar Teun , ten Brink Corlinda B. , van Kooten Peter J. , Hauet‐Broeren Femke , Ludanyi Katalin , van Eden Willem , Broeren Chris P. , Glant Tibor T.
Published: July 2006

Objective

To better understand the role of antigen (arthritogenic epitope)–specific T cells in the development of autoimmune arthritis.

Methods

A transgenic (Tg) mouse expressing the T cell receptor (TCR) Vα1.1 and Vβ4 chains specific for a dominant arthritogenic epitope (designated 5/4E8) of human cartilage proteoglycan (HuPG) aggrecan was generated. This TCR‐Tg mouse strain was backcrossed into the PG‐induced arthritis (PGIA)–susceptible BALB/c strain and tested for arthritis incidence and severity.

Results

CD4+ TCR‐Tg T cells carried functionally active TCR specific for a dominant arthritogenic epitope of HuPG (5/4E8). T cells of naive TCR‐Tg mice were in an activated stage, since the in vitro response to HuPG or to peptide stimulation induced interferon‐γ and interleukin‐4 production. TCR‐Tg mice uniformly, without exception, developed severe and progressive polyarthritis, even without adjuvant. Inflamed joints showed extensive cartilage degradation and bone erosions, similar to that seen in the arthritic joints of wild‐type BALB/c mice with PGIA. Spleen cells from both naive and HuPG‐immunized arthritic TCR‐Tg mice could adoptively transfer arthritis when injected into syngeneic BALB/c.SCID recipient mice.

Conclusion

TCR‐Tg BALB/c mice display increased arthritis susceptibility and develop aggravated disease upon in vivo antigen stimulation. This model using TCR‐Tg mice is a novel and valuable research tool for studying mechanisms of antigen (arthritogenic epitope)–driven regulation of arthritis and understanding how T cells recognize autoantigen in the joints. This type of mouse could also be used to develop new immunomodulatory strategies in T cell–mediated autoimmune diseases.
Mechanistic Investigation of the Oxygen‐Atom‐Transfer Reactivity of Dioxo‐molybdenum(VI) Complexes
Authors: Kail Brian W. , Pérez Lisa M. , Zarić Snežana D. , Millar Andrew J. , Young Charles G. , Hall Michael B. , Basu Partha
Published: July 2006

The oxygen‐atom‐transfer (OAT) reactivity of [LiPrMoO2(OPh)] (1, LiPr=hydrotris(3‐isopropylpyrazol‐1‐yl)borate) with the tertiary phosphines PEt3 and PPh2Me in acetonitrile was investigated. The first step, [LiPrMoO2(OPh)]+PR3→[LiPrMoO(OPh)(OPR3)], follows a second‐order rate law with an associative transition state (PEt3, ΔH ≠=48.4 (±1.9) kJ mol−1, ΔS ≠=−149.2 (±6.4) J mol−1 K−1, ΔG ≠=92.9 kJ mol−1; PPh2Me, ΔH ≠=73.4 (±3.7) kJ mol−1, ΔS ≠=−71.9 (±2.3) J mol−1 K−1, ΔG ≠=94.8 kJ mol−1). With PMe3 as a model substrate, the geometry and the free energy of the transition state (TS) for the formation of the phosphine oxide‐coordinated intermediate were calculated. The latter, 95 kJ mol−1, is in good agreement with the experimental values. An unexpectedly large O‐P‐C angle calculated for the TS suggests that there is significant O‐nucleophilic attack on the PC σ* in addition to the expected nucleophilic attack of the P on the MoO π*. The second step of the reaction, that is, the exchange of the coordinated phosphine oxide with acetonitrile, [LiPrMoO(OPh)(OPR3)] + MeCN → [LiPrMoO(OPh)(MeCN)] + OPR3, follows a first‐order rate law in MeCN. A dissociative interchange (Id) mechanism, with activation parameters of ΔH ≠=93.5 (±0.9) kJ mol−1, ΔS ≠=18.2 (±3.3) J mol−1 K−1, ΔG ≠=88.1 kJ mol−1 and ΔH ≠=97.9 (±3.4) kJ mol−1, ΔS ≠=47.3 (±11.8) J mol−1 K−1, ΔG ≠=83.8 kJ mol−1, for [LiPrMoO(OPh)(OPEt3)] (2 a) and [LiPrMoO(OPh)(OPPh2Me)] (2 b), respectively, is consistent with the experimental data. Although gas‐phase calculations indicate that the MoOPMe3 bond is stronger than the MoNCMe bond, solvation provides the driving force for the release of the phosphine oxide and formation of [LiPrMoO(OPh)(MeCN)] (3).
Apoptolidin A: Total Synthesis and Partially Glycosylated Analogues
Authors: Wehlan Hermut , Dauber Mario , Fernaud M. Teresa Mujica , Schuppan Julia , Keiper Sonja , Mahrwald Rainer , Garcia M.‐Elisa Juarez , Koert Ulrich
Published: July 2006

The total synthesis of apoptolidin A is described employing an early glycosylation strategy. Strategic disconnections were chosen between C11–C12 (cross‐coupling) and C19O–C1 (macrocyclization). The cis‐selective glycosylation at C9‐OH was achieved with the new SIBA protective group at O2/O3 of the L‐glucose residue. Auxiliary substitutents at the 2‐position of the 2‐deoxy sugars were applied to form selectively the glycosidic linkages of the C27 disaccharide. The cross‐coupling of the glycosylated northern half with the glycosylated southern half was achieved with CuI‐thiophene carboxylate. The macrocyclization of a trihydroxy carboxylic acid produced the 20‐membered macrolide selectively. H2SiF6 was suitable for the final deprotection of the silyl ethers and the conversion of the C21 methylketal into the hemiketal. The synthetic flexibility of the approach was proven by the synthesis of some glycovariants.
Effect of the Complexant Shape on the Large First Hyperpolarizability of Alkalides Li+(NH3)4M−
Authors: Jing Ying‐Qi , Li Zhi‐Ru , Wu Di , Li Ying , Wang Bing‐Qiang , Gu Feng Long , Aoki Yuriko
Published: July 2006

The effect of complexant shape effect on the first hyperpolarizability β0 of alkalides Li+(NH3)4M− (M=Li, Na, K) was explored. At the MP2/6‐311++G level, Li+(NH3)4M− (M=Li, Na, K) have considerable β0 values due to excess electrons from chemical doping and charge transfer. By comparison with the alkalides Li+(calix[4]pyrrole)M−, a complexant shape effect in Li+(NH3)4M− is detected. The β0 values of Li+(NH3)4M− with the “smaller”, inorganic, Td‐symmetric (NH3)4 complexant are more than four times larger than those of Li+(calix[4]pyrrole)M− with the “larger”, organic C4v‐symmetric calix[4]pyrrole complexant. The ratios of the β0 values of Li+(NH3)4M− and Li+(calix[4]pyrrole)M− are 6.57 (M=Li ), 6.55 (M=Na), and 5.17 (M=K). In the Li+(NH3)4M− systems, the NBO charge and oscillator strength are found to monotonically depend on the atomic number of the alkali metal anion. The order of the NBO charges of the alkali anions M− is −0.667 (M=Li )>−0.644 (M=Na)>−0.514 (M=K), while the order of the oscillator strengths in the crucial transition is 0.351 (M=Li )<0.360 (M=Na)<0.467 (M=K). This indicates that complexant shape effects are strong, and consequently the β0 values of Li+(NH3)4M− are found to be β0=70 295 (M=Li )<96 780 (M=Na)<185 805 a.u. (M=K). This work reveals that the use of a high‐symmetry complexant is an important factor that should be taken into account when enhancing the first hyperpolarizability of alkalides by chemical doping.
Growing Graphene Sheets from Reactions with Methyl Radicals: A Quantum Chemical Study
Authors: Carissan Yannick , Klopper Wim
Published: July 2006

Hydrogen abstraction reactions by methyl radicals on the zigzag and armchair edges of perylene are studied by density functional theory (DFT) to explore various growth pathways that seem to be in line with experimental observations. The DFT approach is validated by comparing the results obtained from calculations with six different functionals with those obtained from correlated ab initio methods, thereby emphasizing the calculation of reaction barriers. A useful compromise between accuracy and computational cost is provided by DFT, and possible pathways are studied in detail at this level of calculation. Our computational study is carried out by ordering, as a first step, all of the isomers that arise from the abstraction of one or two H atoms from 1,12‐dimethyl‐1,12‐dihydroperylene and 3,4‐dimethyl‐3,4‐dihydroperylene with respect to their energies. Subsequently, only those pathways that connect low‐energy isomers are investigated. The calculations reveal that the selected pathways are favored thermodynamically, and also that the reaction barriers are somewhat higher than the energy locally available for the respective reaction. Notably, in the case of 3,4‐dimethyl‐3,4‐dihydroperylene, the first two reaction steps have no or only a very low reaction barrier. The final conclusion of our study is that a cascade of reactions is possible that leads to the growth of a graphene sheet on a graphite surface.
Fat‐body remodeling in Drosophila melanogaster
Authors: Nelliot Archana , Bond Nichole , Hoshizaki Deborah K.
Published: July 2006

The remodeling of the larval fat body is observed in many insects during metamorphosis, but little is known about the physiological importance or the regulation of this process. In Drosophila melanogaster, fat‐body remodeling involves the dissociation of the fat body into individual fat cells, which persist throughout pupal development but are later removed by cell death in the young adult. Inhibition of fat‐body dissociation is associated with pharate adult lethality and thus is likely to be an essential developmental event. As a start toward understanding the role of fat‐body remodeling in the life history of insects, we carried out a detailed study of fat‐body disassociation in D. melanogaster using fluorescent microscopy, and tested whether this process is mediated by hemocytes as proposed for fat‐body remodeling in Sarcophaga peregrina. We identified and correlated stereotypic events in fat‐body dissociation with developmental changes during metamorphosis, and have demonstrated by cell ablation studies that fat‐body remodeling in D. melanogaster is a hemocyte independent process. genesis 44:396–400, 2006. Published 2006 Wiley‐Liss, Inc.
Assessment of the performance of density‐functional methods for calculations on iron porphyrins and related compounds
Authors: Liao Meng‐Sheng , Watts John D. , Huang Ming‐Ju
Published: July 2006

The behaviors of a large number of GGA, meta‐GGA, and hybrid‐GGA density functionals in describing the spin‐state energetics of iron porphyrins and related compounds have been investigated. There is a large variation in performance between the various functionals for the calculations of the high‐spin state relative energies. Most GGA and meta‐GGA functionals are biased toward lower‐spin states and so fail to give the correct ground state for the high‐spin systems, for which the meta‐GGA functionals show more or less improvement over the GGA ones. The GGA functionals that use the OPTX correction for exchange show remarkably high performance for calculating the high‐spin state energetics, but their results for the intermediate‐spin states are somewhat questionable. A heavily parameterized GGA functional, HCTH/407, provides results which are in qualitative agreement with the experimental findings for the iron porphyrins [FeP, FeP(Cl), FeP(THF)2], but its relative energies for the high‐spin states are probably somewhat too low. The high‐spin state relative energies are then even more underestimated by the corresponding meta‐GGA functional τ‐HCTH. For the hybrid‐GGA functionals, the Hartree‐Fock (HF)‐type (or exact) exchange contribution strongly stabilizes the high‐spin states, and so the performance of such functionals is largely dependent upon the amount of the HF exchange admixture in them. The B3LYP, B97, B97‐1, and τ‐HCTH‐hyb functionals are able to provide a satisfactory description of the energetics of all the systems considered. © 2006 Wiley Periodicals, Inc. J Comput Chem 27:1577–1592, 2006
Efficiency and accuracy of the elongation method as applied to the electronic structures of large systems
Authors: Makowski Marcin , Korchowiec Jacek , Gu Feng Long , Aoki Yuriko
Published: July 2006

Current state of development of the elongation method originally proposed by Imamura is presented. Recent progress in methodology, including geometry optimization and employment of the fast multiple method, is highlighted. The accuracy and efficiency of the elongation method as compared to exact canonical Hartree–Fock and Kohn–Sham approaches are discussed. Potential applications are illustrated by wide range of calculations for model systems. The elongation calculations are demonstrated to be much more efficient compared to the conventional ones with high accuracy maintained. The elongation CPU time is shown by the model calculations as linear or sub‐linear scaling for quasi‐one‐dimensional systems. Future work of development into post‐Hartree–Fock methodologies are pointed out. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1603–1619, 2006