bluuebunny/crossref_metadata_2025 huggingface dataset:
Health‐related quality of life over time since resective epilepsy surgery
Authors: Spencer Susan S. , Berg Anne T. , Vickrey Barbara G. , Sperling Michael R. , Bazil Carl W. , Haut Sheryl , Langfitt John T. , Walczak Thaddeus S. , Devinsky Orrin
Published: June 2007

Objective

Health‐related quality of life (HRQOL) improves after resective epilepsy surgery, but data are limited to short follow‐up in mostly retrospective reports, with minimal consideration of other potential factors that might influence HRQOL.

Methods

In a prospective multicenter study, 396 patients underwent resective epilepsy surgery. They completed the Quality of Life in Epilepsy Inventory‐89 (QOLIE‐89) before surgery, within 6 months, and at approximately yearly intervals after surgery. Seizure outcome was ascertained by phone calls every 3 months, and dates of postoperative seizures were chronicled. Overall HRQOL as measured by the QOLIE‐89 was evaluated with respect to seizure outcome using logistic regression.

Results

QOLIE‐89 scores increased significantly at the first postoperative measurement (within 6 months after surgery) in the cohort overall; subsequent changes over time were sensitive to seizure‐free and aura‐free status. After adjusting for baseline scores, the corresponding postsurgical QOLIE‐89 overall, and four dimension scores, increased as a function of square root of time seizure‐free, and independently as a function of square root of time aura free, leveling by 2 years of stable seizure (aura) status. HRQOL was not independently related to duration of epilepsy, duration of intractable epilepsy, or continuation of medications.

Interpretation

HRQOL improves early after surgery, regardless of seizure outcome. Subsequent changes parallel length of time seizure free or aura free, stabilize after 2 years, and are unrelated to duration of epilepsy, duration of intractable epilepsy, or continued medication use. Ann Neurol 2007
Synthesis and reactions of a novel bulky aryllithium
Authors: Saito Masaichi , Okuyama Yuta , Tajima Tomoyuki , Kato Daichi , Yoshioka Michikazu
Published: June 2007

A novel bulky aryllithium, 2,6‐bis{2,5‐bis[bis(trimethylsilyl)methyl]phenyl}phenyllithium (BbspLi), was synthesized. Reactions of BbspLi 5 with Group 14 electrophiles, such as stannous chloride, with carbon tetrachloride or tetrachlorometallanes gave fluorene 6. Reaction of BbspLi with carbon tetrachloride gave benzyl chloride 8, which converted to 6 under acidic conditions. BbspLi 5 isomerized to the corresponding benzyl anion 10, which underwent halophilic reactions with Group 14 electrophiles to give fluorene 6 via the benzyl chloride intermediate 8. Copyright © 2007 John Wiley & Sons, Ltd.
Alkynylorganotins, versatile precursors of class II hybrid materials
Authors: Toupance Thierry , de Borniol Mervyn , Hamzaoui Hicham El , Jousseaume Bernard
Published: June 2007

In the field of functional organic–inorganic hybrid materials, recent trends in the chemistry based on trialkynylorganotins 1 and organically bridged α,ω‐bis(trialkynyltin) compounds 2 are reviewed. Compounds 1 reacted with non‐porous silica and nanoporous tin dioxide powders to yield hydrophobic, lipophobic or perylene dye‐modified oxide materials. The formation of MoxideOSnC bonds and the release of three molecules of alkyne led to the irreversible chemisorption of 1, the reaction rate and the chain loading depending on the electronic demand and the bulkiness of the organic group grafted. Furthermore, self‐assembled tin‐based class II hybrid materials were spontaneously formed by hydrolysis of 2 under homogeneous conditions as the two tin atoms were bridged through a rigid or a semi‐rigid linker. Subsequent thermal treatment of these hybrids under an oxygen flow at 400–500 °C furnished nanoporous tin dioxide materials consisting of a porous network of aggregated cassiterite tin dioxide particles. An unusual polymodal distribution of mesopore sizes was found in the case of the sample prepared from the hybrid containing the diphenylene spacer. Copyright © 2007 John Wiley & Sons, Ltd.
Supramolecular aspects of tin and lead chemistry
Authors: Haiduc Ionel
Published: June 2007

Cross‐fertilization between organometallic and supramolecular chemistry opens new ways of understanding and interpreting the solid state structures, leading to a distinct new discipline. Intermolecular interactions of various types occur in solid state, leading to self‐assembly and self‐organization of organometallic molecular species. Self‐assembly through hydrogen bonds, dative (coordinate) bonds, soft‐soft (secondary bond) and pi‐bond interactions, illustrate the great diversity of the bonding motifs available for supramolecular self‐assembly in organotin and organolead chemistry. Copyright © 2007 John Wiley & Sons, Ltd.
Synthesis and structures of M(Me3SiNCHNSiMe3)3 (M = Al, Ga) via reactions of M‐hydrides with Me3SiNCNSiMe3
Authors: Ritter Cole , Chizmeshya Andrew V. G. , Gray T. L. , Kouvetakis J.
Published: June 2007

Reactions of LiAlH4 and LiGaH4 with Me3SiNCNSiMe3 yield, respectively, the monomeric hexacoordinate Al(Me3SiNCHNSiMe3)3 (1) and Ga(Me3SiNCHNSiMe3)3, (2) metal amidinate compounds. A unique feature of the work is the creation of the previously unknown bidentate [Me3SiNCHNSiMe3] anion ligand which shows the propensity to fully encapsulate the Al and Ga metal centers despite potential steric crowding associated with the six‐fold coordination. Compound 1 was also obtained by the reaction of (Me3N)AlH3 with Me3SiNCNSiMe3 via displacement of NMe3 followed by reduction of the carbodiimide group. The structural properties of 1 and 2 derived from single crystal X‐ray diffraction are elucidated and compared with various coordination analogs. Copyright © 2007 John Wiley & Sons, Ltd.
Formation of the first injectable poly(vinyl alcohol) hydrogel by mixing of functional PVA precursors
Authors: Ossipov Dmitri A. , Brännvall Karin , Forsberg‐Nilsson Karin , Hilborn Jöns
Published: June 2007

In this study we describe the development of an injectable, in situ chemical hydrogel forming system. The gelation occurs under neutral pH and at room temperature immediately upon mixing of the two aqueous poly (vinyl alcohol) components specifically derivatized through carbamate linkages with aldehyde (PVA‐AL) and hydrazide (PVA‐HY) functional groups, respectively. Aldehyde and hydrazide pendant groups were incorporated with a low degree of substitution (DS) into the PVA backbone to keep PVA structural homogeneity minimally altered. As a result, the hydrazone crosslinks are formed rapidly between aldehyde and hydrazide pendant groups when the correspondingly modified PVA components are brought in contact as water solutions. To assess in situ hydrazone crosslinks formation for in vitro cytocompatibility, murine neuroblastoma N2a cells were suspended in cell culture medium with the dissolved PVA‐HY prior to addition to the PVA‐AL aqueous solution. Thus, the cells were chemically encapsulated in a polymer network that was formed by mixing of the corresponding aqueous solutions of PVA functional precursors. Biochemical analysis revealed that cells survived chemical crosslinking and remained viable in the hydrogel for 4 days of culture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007
Nuclear localization and DNA binding of ecdysone receptor and ultraspiracle
Authors: Cronauer M.V. , Braun S. , Tremmel Ch. , Kröncke K.‐D. , Spindler‐Barth M.
Published: June 2007

The Ecdysone receptor (EcR) is distributed between cytoplasm and nucleus in CHO cells. Nuclear localization is increased by the ligand Muristerone A. The most important heterodimerization partner Ultraspiracle (Usp) is localized predominantly in the nucleus. We used the diethylentriamine nitric oxide adduct DETA/NO, which releases NO and destroys the zinc‐finger structure of nuclear receptors, to investigate whether nuclear EcR and Usp interact with DNA. If expressed separately, Usp and EcR in the absence of hormone do not interact with DNA. The hormone‐induced increase in nuclear EcR is due to enhanced DNA binding. In the presence of Usp, EcR is shifted nearly quantitatively into the nucleus. Only a fraction (approximately 30%) of the heterodimer is sensitive to DETA/NO. Interaction of the heterodimer with DNA is mediated mainly by the C‐domain of EcR. Deletion of the DNA‐binding domain of Usp only slightly reduces nuclear localization of EcR/Usp, although the nuclear localization signal of Usp is not present anymore. The results indicate that EcR and Usp can enter the nucleus independently, but cotransport of both receptors mediated by dimerization via the ligand binding domains is possible even in the absence of hormone. Arch. Insect Biochem. Physiol. 65:125–133, 2007. © 2007 Wiley‐Liss, Inc.
Nucleocytoplasmic shuttling of the ecdysteroid receptor (EcR) and of ultraspiracle (Usp) from Drosophila melanogaster in mammalian cells: Energy requirement and interaction with exportin
Authors: Betanska Katarzyna , Nieva Claudia , Spindler‐Barth Margarethe , Spindler Klaus‐Dieter
Published: June 2007

The small G protein Ran, which is important for nucleocytoplasmic shuttling of proteins is present, but does not interact with EcR, Usp, and EcR/Usp. As shown by oligomycin treatment, EcR, Usp, and EcR/Usp import is energy dependent. Export of EcR and EcR/Usp is mediated by exportin‐1 (CRM‐1) as shown by the inhibiting effect of leptomycin B (LMB). Usp remains in the nucleus for more than 24 h. Nuclear retainment of EcR and Usp is energy dependent as shown by treatment with oligomycin. No export signal could be identified for Usp. The data confirm that EcR and Usp can enter the nucleus independently and that intracellular localization is regulated individually for each receptor. It is also demonstrated that the export signal of EcR is inaccessible after heterodimerization with Usp. Arch. Insect Biochem. Physiol. 65:134–142, 2007. © 2007 Wiley‐Liss, Inc.
Applications of EcR gene switch technology in functional genomics
Authors: Tavva Venkata S. , Palli Subba R. , Dinkins Randy D. , Collins Glenn B.
Published: June 2007

Genetic engineering of plants using transgenic technology is targeted to enhance agronomic performance or improved quality traits in a wide variety of plant species, and has become a fundamental tool for basic research in plant biotechnology. Constitutive promoters are presently the primary means used to express transgenes in plants. However, inducible gene regulation systems based on specific chemicals have many potential applications in agriculture and for enhancing the basic understanding of gene function. As a result, several gene switches have been developed. The ecdysone receptor gene switch is one of the best inducible gene regulation systems available, because the chemical, methoxyfenozide, required for its regulation is registered for field use. An EcR gene switch with a potential for use in large‐scale field applications has been developed by adopting a two‐hybrid format. In a two‐hybrid switch format, the GAL4 DNA binding domain (GAL4 DBD) was fused to the ligand binding domain (LBD) of the Choristoneura fumiferana ecdysone receptor (CfEcR); and, the VP16 activation domain (VP16 AD) was fused to the LBD of Locust migratoria retinoid X receptor (LmRXR). The sensitivity of the CfEcR gene switch was improved from micromolar to nanomolar concentrations of ligand by using the CfEcR:LmRXR two‐hybrid switch. In this report, we demonstrate the utility of CfEcR:LmRXR two‐hybrid gene switch in functional genomics applications for regulating the expression of a Superman‐like single zinc finger protein 11 (ZFP11) gene in both Arabidopsis and tobacco transgenic plants. Arch. Insect Biochem. Physiol. 65:164–179, 2007. © 2007 Wiley‐Liss, Inc.
FeCl3‐Catalyzed Addition of 1,3‐Dicarbonyl Compounds to Aromatic Olefins
Authors: Kischel Jette , Michalik Dirk , Zapf Alexander , Beller Matthias
Published: June 2007

A direct, intermolecular addition of 1,3‐dicarbonyl compounds to styrenes in the presence of FeCl3 as an inexpensive and disposable catalyst has been developed for the straightforward and practical synthesis of arylated diketones and ketoesters. The reactions proceed under mild conditions for most substrates (50–80 °C), and no strong acid or base is required. The synthetic value of the method is demonstrated by 15 examples, including the synthesis of the current pharmaceutical drug warfarin in one step and 42 % yield from commercially available substrates.
Contribution of specific binding to the central benzodiazepine site to the brain concentrations of two novel benzodiazepine site ligands
Authors: Pike Andrew , Cook Susan M. , Watt Alan P. , Scott‐Stevens Paul , Rosahl Thomas W. , McKernan Ruth M. , Pym Luanda J. , Guiblin Alec , Moyes Christopher , Sohal Bindi , Atack John R.
Published: June 2007

Thein vivooccupancy of brain benzodiazepine binding sites by compounds A and B was measured using a [3H]Ro 15‐1788 binding assay and related to plasma and brain drug concentrations. The plasma concentration associated with 50% occupancy was higher for compound A than compound B (73 and 3.7 nM, respectively), however, there was little difference in the brain concentrations required (73 and 63 nM). Both compounds showed a non‐linear relationship between plasma and brain concentrations such that above brain concentrations of ∼100 nMincreasing plasma concentrations did not result in a concomitant increase in brain concentrations. This is consistent with brain concentrations being dependent on a saturable compartment which was postulated to be the benzodiazepine binding site‐containing GABAAreceptors. This hypothesis was tested in α1H101R mice, in which the α1 subunit of the GABAAreceptor is rendered insensitive to benzodiazepine binding resulting in an approximate 50% reduction in the total benzodiazepine‐containing GABAAreceptor population. It was shown that the Occ50brain concentrations in the α1H101R animals was lower (17 nM) than in wild type mice (63 nM), as was the plateau concentration in the brain (105 and 195 nM, respectively). These data suggest measured concentrations of compounds A and B in brain tissue are dependent on receptor expression with a minimal contribution from unbound and non‐specifically bound compound. Copyright © 2007 John Wiley & Sons, Ltd.
Pharmacokinetic aspects of naloxone‐precipitated morphine withdrawal in male and female prepubertal mice
Authors: Diaz Silvina L. , Hermida María P. , Joannas Leonel D. , Olivera Mónica , Ridolfi Adriana , Villaamil Edda C. , Balerio Graciela N.
Published: June 2007

It has been shown that the expression of the morphine (MOR) withdrawal syndrome precipitated by naloxone (NAL) is more intense in male mice than in females, but the reasons for this phenomenon remain uncertain. The purpose of the present study was to evaluate whether this sexual dimorphism might be due to differences in MOR and/or NAL plasma levels after a chronic treatment with MOR. Prepubertal Swiss male and female mice were rendered dependent by intraperitoneal (i.p.) injection of MOR (2 mg/kg), twice daily for 9 days. On day 10 dependent mice received NAL (6 mg/kg, i.p.) 60 min after MOR injection. Blood samples were taken at different times in order to determine MOR and NAL plasma levels by gas chromatography‐mass spectrometry (GC‐MS) and high‐performance liquid chromatography (HPLC), respectively. Pharmacokinetic analysis showed no differences between male and female mice either for MOR or for NAL. In conclusion, although males and females respond differentially to NAL‐precipitated withdrawal, this dimorphic behavior would not be influenced by a pharmacokinetic factor. Copyright © 2007 John Wiley & Sons, Ltd.
Evaluation of the developmental toxicity of lenalidomide in rabbits
Authors: Christian Mildred S. , Laskin Oscar L. , Sharper Valerie , Hoberman Alan , Stirling David I. , Latriano Louise
Published: June 2007

BACKGROUND: Lenalidomide, a thalidomide analog, is indicated for treatment of patients with deletion‐5q myelodysplastic syndromes or multiple myeloma. NZW rabbits were used because of sensitivity to thalidomide's teratogenicity. METHODS: Range‐finding and pulse‐dosing studies preceded a full developmental toxicity study in New Zealand white (NZW) rabbits (25/group) given lenalidomide (0, 3, 10, or 20 mg/kg/day) or thalidomide (180 mg/kg/day) by stomach tube on gestation days (GD) 7–19. Clinical signs, body weights, and feed consumption were recorded daily from GD 7. On GD 29, standard maternal necropsy, uterine content, and fetal evaluations were carried out. RESULTS: In all studies, thalidomide was selectively toxic to development. In the pulse‐dosing study, lenalidomide did not affect development at 100 mg/kg/day. Increases in Cmax and AUC0–24 hr values for lenalidomide were slightly less than dose‐proportional; lenalidomide occurred in the fetuses. At 10 and 20 mg/kg/day, lenalidomide was maternally toxic (reduced body weight gain and feed consumption; at 20 mg/kg/day, weight loss and one abortion). Developmental toxicity at 10 and 20 mg/kg/day included reduced fetal body weights and increased postimplantation losses and fetal variations (morbidity/purple‐discolored skin, undeveloped intermediate lung lobe, irregular nasal‐frontal suture, and delayed metacarpal ossification). Thalidomide selectively reduced fetal body weight, increased postimplantation loss and caused characteristic limb and other dysmorphology. CONCLUSIONS: The maternal and developmental NOAELs for lenalidomide are 3 mg/kg/day. Unlike thalidomide, lenalidomide affected embryo–fetal development only at maternally toxic dosages, confirming that structure‐activity relationships may not predict maternal or developmental effects. No fetal malformations were attributable to lenalidomide. Birth Defects Res (Part B), 2007. © 2007 Wiley‐Liss, Inc.
Histologic changes in ovary, uterus, vagina, and mammary gland of mature beagle dogs treated with the SERM idoxifene
Authors: Rehm Sabine , Solleveld Henk A. , Portelli Samm T. , Wier Patrick J.
Published: June 2007

BACKGROUND: Idoxifene is a selective estrogen receptor modulator similar to tamoxifen but is no longer in pharmaceutical development due to adverse genitourinary effects in the clinic. Histologic observations of the reproductive system and mammary glands are presented from female dogs treated with idoxifene for up to 12 months. METHODS: Studies were conducted as part of regulatory requirements to support clinical development. Idoxifene was given orally by capsule, once daily, for 1, 6, or 12 months to female Beagle dogs (n = 3 or 4/group) aged 11–14 months (start of dosing) at dosages 0, 0.03, 0.3, 1.5, or 3 mg/kg/day. Evaluations included the following: clinical observations, hematology, hemostasis, chemistry, toxicokinetics, and histology. RESULTS: Dose‐ and time‐dependent findings were present in dogs given ≥0.03 mg/kg/day and included abnormal vaginal discharge, minor increases of platelet and neutrophil counts, and microscopic observations in the ovary (atrophy and mesothelial [ovarian surface epithelium] hyperplasia), endometrium (edema, inflammation, glandular atrophy, squamous metaplasia, increased collagen), myometrium (edema, increased collagen), vagina (squamous hyperplasia, keratinization), and mammary gland (atrophy). CONCLUSION: Dogs given idoxifene exhibited estrogenic effects in ovary, uterus(), and vagina but antiestrogenic effects in endometrial and mammary glands consistent with several observations in clinical trials in post‐menopausal women treated with triphenylethylenes. Birth Defects Res (Part B), 2007. © 2007 Wiley‐Liss, Inc.
Evaluating rodent vaginal and uterine histology in toxicity studies
Authors: Li Shaunfang , Davis Barbara
Published: June 2007

Interpreting histopathology of the female rodent reproductive tract can be challenging in toxicity studies. However, diagnosis can be relatively uncomplicated with an understanding of the relationship between form and function. We describe this relationship for the rodent uterus and vagina and discuss some strategies to simplify diagnosis. Birth Defects Res (Part B), 2007. © 2007 Wiley‐Liss, Inc.
Identification of drug‐induced hyper‐ or hypoprolactinemia in the female rat based on general and reproductive toxicity study parameters
Authors: Rehm Sabine , Stanislaus Dinesh J. , Wier Patrick J.
Published: June 2007

Observations associated with drug‐induced hyper‐ or hypoprolactinemia in rat toxicology studies may be similar and include increased ovarian weight due to increased presence of corpora lutea. Hyperprolactinemia may be distinguished if mammary gland hyperplasia with secretion and/or vaginal mucification is observed. Reproductive toxicity study endpoints can differentiate hyper‐ from hypoprolactinemia based on their differential effects on estrous cycles, mating, and fertility. Although the manifestations of hyper‐ and hypoprolactinemia in rats generally differ from that in humans, mechanisms of drug‐related changes in prolactin synthesis/release can be conserved across species and pathologically increased or decreased prolactin levels may compromise some aspect of reproductive function in all species. Birth Defects Res (Part B), 2007. © 2007 Wiley‐Liss, Inc.
Investigation of protein expression in magnetic field‐treated human glioma cells
Authors: Kanitz M.H. , Witzmann F.A. , Lotz W.G. , Conover D. , Savage R.E.
Published: June 2007

We previously reported phenotypic changes in human breast cancer cells following low‐level magnetic field (MF) exposure. Here proteomic methods were used to investigate the biochemical effect of MF exposure in SF767 human glioma cells. Protein alterations were studied after exposure to 1.2 microTesla (µT) MF [12 milliGauss (mG), 60 Hertz (Hz)] ± epidermal growth factor (EGF). SF767 cells were exposed for 3 h to sham conditions (<0.2 µT ambient field strength) or 1.2 µT MF (±EGF; 10 ng/ml). Solubilized protein fractions (sham; 1.2 µT; sham + EGF; 1.2 µT + EGF) were loaded for electrophoresis by 2D‐PAGE and stained using a colloidal Coomassie blue technique to resolve and characterize the proteins. Protein patterns were compared across groups via Student's t‐test using PDQUEST software. Cell profiles revealed significant alterations in the spot density of a subset of treated cells. Automated spot excision and processing was performed prior to peptide mass fingerprinting proteins of interest. Fifty‐seven proteins from the detectable pool were identified and/or found to differ significantly across treatment groups. The mean abundance of 10 identified proteins was altered following 1.2 µT exposure. In the presence of EGF six proteins were altered after low magnetic field treatment by increasing (4) or decreasing (2) in abundance. The results suggest that the analysis of differentially expressed proteins in SF767 cells may be useful as biomarkers for biological changes caused by exposure to magnetic fields. Bioelectromagnetics 28:546–552, 2007. © 2007 Wiley‐Liss, Inc.
Alltagswissen – Körperwissen – Praxiswissen – Fachwissen. Zur Aneignung, Bewertungs‐ und Orientierungslogik von Wissenskulturen
Authors: Labouvie Eva
Published: June 2007

Everyday knowledge – body knowledge – knowledge of experience – specialized knowledge: Acquisition, assessment and the orientation of logic concerning cultures of knowledge. – The essay explores changes in the understanding, legitimisation, and practice of midwifery. It was one of the earliest professional activities for women. During the eighteenth century a new culture of expertise emphasized theoretical knowledge and adherence to medical disciplines over the empirical practice gained by women. This early phase of professionalisation, with its hierarchies and preferred use of medically accredited knowledge, was not, however, solely divided along gender lines. Female professionalism was not just supplanted by male academic medicalisation. New ways of attaining and assessing knowledge, a different perception of how it is organised, and above all, social change created new patterns of understanding. This process achieved a new professional ethos. In pursuing the issue of gender, various examples are chosen to illustrate how changes in scientific knowledge and its relevant application are mediated. The construct of scientific knowledge and how it is used reflects gender relations and power structures. There is not only competition between female and male perceptions of knowledge, but also male stereotyping of female knowledge, in particular male notions of what kind of knowledge is necessary and how this is perceived by women. Karen Offen used the term ‘knowledge wars’ to describe how a monopoly of scientific expertise and relevant knowledge works within the professions.
Von Vielschichtigkeiten und Verschränkungen “Kulturen der Wissenschaft – Wissenschaften in der Kultur”
Authors: Ash Mitchell
Published: June 2007

On Multiple Levels and Linkages: Introduction to the Symposium ‘Cultures of Sciences – the Sciences in Culture’. – The article presents briefly approaches to cultural history and cultural studies that seem potentially useful to or have recntly been applied in historical studies of the sciences. The first section discusses three such approaches: discourse analysis, symbolic artefacts (images and text), and cultures of scientific practice. Each of the three approaches raises issues of its own, and all of them share a common problem characteristic of cultural and social history in general: linking micro and macro levels of analysis. The second section presents three approaches to resolving this dilemma by focusing on specific linkages between cultures of science (or culture in the sciences) and general history: scientific thought and practice as norms for professional behavior, for example in fields of knowledge dominated by women; spaces of knowledge, for example the city; and linkages of cultural, media and economic history in fields such as radio and television.
Sample Size Reestimation by Bayesian Prediction
Authors: Wang Ming‐Dauh
Published: June 2007

We review a Bayesian predictive approach for interim data monitoring and propose its application to interim sample size reestimation for clinical trials. Based on interim data, this approach predicts how the sample size of a clinical trial needs to be adjusted so as to claim a success at the conclusion of the trial with an expected probability. The method is compared with predictive power and conditional power approaches using clinical trial data. Advantages of this approach over the others are discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Under‐Smoothed Kernel Confidence Intervals for the Hazard Ratio Based on Censored Data
Authors: Tu Dongsheng
Published: June 2007

In cancer clinical trials, it is often of interest in estimating the ratios of hazard rates at some specific time points during the study from two independent populations. In this paper, we consider nonparametric confidence interval procedures for the hazard ratio based on kernel estimates for the hazard rates with under‐smoothing bandwidths. Two methods are used to derive the confidence intervals: one based on the asymptotic normality of the ratio of the kernel estimates for the hazard rates in two populations and another through Fieller's Theorem. The performances of the proposed confidence intervals are evaluated through Monte‐Carlo simulations and applied to the analysis of data from a clinical trial on early breast cancer. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Parent training for children with pervasive developmental disorders: a multi‐site feasibility trial
Authors:   Research Units on Pediatric Psychopharmacology [RUPP] Autism Network
Published: June 2007

The primary purpose of this study was to evaluate the feasibility of a structured, manual‐based parent training (PT) program designed to reduce noncompliant behavior and enhance adaptive behavior in children with Pervasive Developmental Disorders (PDD) who were taking medication for irritability, tantrums, aggression, and self‐injury. Children (N = 17, mean age 7.7 ± 2.6 years) with PDD were enrolled in a 24‐week structured PT protocol. Parental attendance to sessions (93%), satisfaction with the program (92%), and adherence to PT assignments (80%) were excellent. The program was adequately implemented with a mean treatment integrity rate of 94%. Parent‐reported rates of noncompliance were reduced by 39%; irritability was reduced by 34%; and daily living skills were enhanced by 19%. Parenting stress was also reduced by 14%. However, these results must be interpreted with caution because the study did not include a control group. The study supports feasibility of the PT program, which will be used in an randomized clinical trials (RCT). Copyright © 2007 John Wiley & Sons, Ltd.
Ligand versus Metal Protonation of an Iron Hydrogenase Active Site Mimic
Authors: Eilers Gerriet , Schwartz Lennart , Stein Matthias , Zampella Giuseppe , de Gioia Luca , Ott Sascha , Lomoth Reiner
Published: June 2007

The protonation behavior of the iron hydrogenase active‐site mimic [Fe2(μ‐adt)(CO)4(PMe3)2] (1; adt=N‐benzyl‐azadithiolate) has been investigated by spectroscopic, electrochemical, and computational methods. The combination of an adt bridge and electron‐donating phosphine ligands allows protonation of either the adt nitrogen to give [Fe2(μ‐Hadt)(CO)4(PMe3)2]+ ([1 H]+), the FeFe bond to give [Fe2(μ‐adt)(μ‐H)(CO)4(PMe3)2]+ ([1 Hy]+), or both sites simultaneously to give [Fe2(μ‐Hadt)(μ‐H)(CO)4(PMe3)2]2+ ([1 HHy]2+). Complex 1 and its protonation products have been characterized in acetonitrile solution by IR, 1H, and 31P NMR spectroscopy. The solution structures of all protonation states feature a basal/basal orientation of the phosphine ligands, which contrasts with the basal/apical structure of 1 in the solid state. Density functional calculations have been performed on all protonation states and a comparison between calculated and experimental spectra confirms the structural assignments. The ligand protonated complex [1 H]+ (pKa=12) is the initial, metastable protonation product while the hydride [1 Hy]+ (pKa=15) is the thermodynamically stable singly protonated form. Tautomerization of cation [1 H]+ to [1 Hy]+ does not occur spontaneously. However, it can be catalyzed by HCl (k=2.2 m−1 s−1), which results in the selective formation of cation [1 Hy]+. The protonations of the two basic sites have strong mutual effects on their basicities such that the hydride (pKa=8) and the ammonium proton (pKa=5) of the doubly protonated cationic complex [1 HHy]2+ are considerably more acidic than in the singly protonated analogues. The formation of dication [1 HHy]2+ from cation [1 H]+ is exceptionally slow with perchloric or trifluoromethanesulfonic acid (k=0.15 m−1 s−1), while the dication is formed substantially faster (k>102 m−1 s−1) with hydrobromic acid. Electrochemically, 1 undergoes irreversible reduction at −2.2 V versus ferrocene, and this potential shifts to −1.6, −1.1, and −1.0 V for the cationic complexes [1 H]+, [1 Hy]+, and [1 HHy]2+, respectively, upon protonation. The doubly protonated form [1 HHy]2+ is reduced at less negative potential than all previously reported hydrogenase models, although catalytic proton reduction at this potential is characterized by slow turnover.
The Stuffed Framework Structure of SrP2N4: Challenges to Synthesis and Crystal Structure Determination
Authors: Karau Friedrich W. , Seyfarth Lena , Oeckler Oliver , Senker Jürgen , Landskron Kai , Schnick Wolfgang
Published: June 2007

SrP2N4 was obtained by high‐pressure high‐temperature synthesis utilizing the multianvil technique (5 GPa, 1400 °C) starting from mixtures of phosphorus(V) nitride and strontium azide. SrP2N4 turned out to be isotypic with BaGa2O4 and is closely related to KGeAlO4. The crystal structure (SrP2N4, a=17.1029(8), c=8.10318(5) Å, space group P63 (no. 173), V=2052.70(2) Å3, Z=24, R(F2)=0.0633) was solved from synchrotron powder diffraction data by applying a combination of direct methods, Patterson syntheses, and difference Fourier maps adding the unit cell information derived from electron diffraction and symmetry information obtained from 31P solid‐state NMR spectroscopy. The structure of SrP2N4 was refined by the Rietveld method by utilizing both neutron and synchrotron X‐ray powder diffraction data, and has been corroborated additionally by 31P solid‐state NMR spectroscopy by employing through‐bond connectivities and distance relations.
Towards a Rational Design of Ruthenium CO2 Hydrogenation Catalysts by Ab Initio Metadynamics
Authors: Urakawa Atsushi , Iannuzzi Marcella , Hutter Jürg , Baiker Alfons
Published: June 2007

Complete reaction pathways relevant to CO2 hydrogenation by using a homogeneous ruthenium dihydride catalyst ([Ru(dmpe)2H2], dmpe=Me2PCH2CH2PMe2) have been investigated by ab initio metadynamics. This approach has allowed reaction intermediates to be identified and free‐energy profiles to be calculated, which provide new insights into the experimentally observed reaction pathway. Our simulations indicate that CO2 insertion, which leads to the formation of formate complexes, proceeds by a concerted insertion mechanism. It is a rapid and direct process with a relatively low activation barrier, which is in agreement with experimental observations. Subsequent H2 insertion into the formateRu complex, which leads to the formation of formic acid, instead occurs via an intermediate [Ru(η2‐H2)] complex in which the molecular hydrogen coordinates to the ruthenium center and interacts weakly with the formate group. This step has been identified as the rate‐limiting step. The reaction completes by hydrogen transfer from the [Ru(η2‐H2)] complex to the formate oxygen atom, which forms a dihydrogen‐bonded RuH⋅⋅⋅HO(CHO) complex. The activation energy for the H2 insertion step is lower for the trans isomer than for the cis isomer. A simple measure of the catalytic activity was proposed based on the structure of the transition state of the identified rate‐limiting step. From this measure, the relationship between catalysts with different ligands and their experimental catalytic activities can be explained.
Oxovanadium(V) Tetrathiacalix[4]arene Complexes and Their Activity as Oxidation Catalysts
Authors: Hoppe Elke , Limberg Christian
Published: June 2007

With the aim of modeling reactive moieties and relevant intermediates on the surfaces of vanadium oxide based catalysts during oxygenation/dehydrogenation of organic substrates, mono‐ and dinuclear vanadium oxo complexes of doubly deprotonated p‐tert‐butylated tetrathiacalix[4]arene (H4TC) have been synthesized and characterized: PPh4[(H2TC)VOCl2] (1) and (PPh4)2[{(H2TC)V(O)(μ‐O)}2] (2). According to the NMR spectra of the dissolved complexes they both retain the structures adopted in the crystalline state, as revealed by single‐crystal X‐ray crystallography. Compounds 1 and 2 were tested as catalysts for the oxidation of alcohols with O2 at 80 °C. Both 1 and 2 efficiently catalyze the oxidation of benzyl alcohol, crotyl alcohol, 1‐phenyl‐1‐propanol, and fluorenol, and in most cases dinuclear complex 2 is more active than mononuclear complex 1. Moreover, the two thiacalixarene complexes 1 and 2 are in many instances more active than oxovanadium(V) complexes containing “classical” calixarene ligands tested previously. Complexes 1 and 2 also show significant activity in the oxidation of dihydroanthracene. Further investigations led to the conclusion that 1 acts as precatalyst that is converted to the active species PPh4[(TC)VO] (3) at 80 °C by double intramolecular HCl elimination. For complex 2, the results of mechanistic investigations indicated that the oxidation chemistry takes place at the bridging oxo ligands and that the two vanadium centers cooperate during the process. The intermediate (PPh4)2[{H2TCV(O)}2(μ‐OH)(μ‐OC13H9)] (4) was isolated and characterized, also with respect to its reactivity, and the results afforded a mechanistic proposal for a reasonable catalytic cycle. The implications which these findings gathered in solution may have for oxidation mechanisms on the surfaces of V‐based heterogeneous catalysts are discussed.
Synthesis, Photophysical and Electrochemical Properties, and Protein‐Binding Studies of Luminescent Cyclometalated Iridium(III) Bipyridine Estradiol Conjugates
Authors: Lo Kenneth Kam‐Wing , Zhang Kenneth Yin , Chung Chi‐Keung , Kwok Karen Ying
Published: June 2007

A new series of luminescent cyclometalated iridium(III) bipyridine estradiol conjugates [Ir(N‐C)2(N‐N)](PF6) (N‐N = 5‐(4‐(17α‐ethynylestradiolyl)phenyl)‐2,2′‐bipyridine, bpy‐est, HN‐C = 2‐phenylpyridine, Hppy (1 a), 1‐phenylpyrazole, Hppz (2 a), 7,8‐benzoquinoline, Hbzq (3 a), 2‐phenylquinoline, Hpq (4 a), 2‐((1,1′‐biphenyl)‐4‐yl)benzothiazole, Hbsb (5 a); N‐N = 4‐(N‐(6‐(4‐(17α‐ethynylestradiolyl)benzoylamino)hexyl)aminocarbonyl)‐4′‐methyl‐2,2′‐bipyridine, bpy‐C6‐est, HN‐C = Hppy (1 b), Hppz (2 b), Hbzq (3 b), Hpq (4 b), Hbsb (5 b)) was synthesized, characterized, and their photophysical and electrochemical properties studied. Upon photoexcitation, all the complexes displayed intense and long‐lived emission in fluid solutions at 298 K and in low‐temperature glass. The emission of complexes 1 a–3 a and 1 b–3 b was assigned to a triplet metal‐to‐ligand charge‐transfer (3MLCT) (dπ(Ir)→π*(bpy‐est and N‐C−)) state mixed with some triplet intraligand (3IL) (π→π*) (N‐C− and N‐N) character. However, the emissive states of the pq− and bsb− complexes 4 a, 4 b, 5 a, and 5 b showed substantial 3IL (π→π*) (pq−/bsb−) character. The lipophilicity of all the complexes was determined by reversed‐phase HPLC. Upon binding to estrogen receptor α, all of these iridium(III) estradiol conjugates exhibited emission enhancement and lifetime extension, rendering them a novel series of luminescent probes for this receptor.
Synthesis, Crystal Structure, and Properties of Two Modifications of MgB12C2.
Authors: Adasch Volker , Hess Kai‐Uwe , Ludwig Thilo , Vojteer Natascha , Hillebrecht Harald
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Structure and Physical Properties of Perovskite Bi0.8Pb0.2NiO3 in Unusual Valence State A4+B2+O3.
Authors: Ishiwata Shintaro , Azuma Masaki , Takano Mikio
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Bulk Ultra‐Fine Eutectic Structure in Ti—Fe—Base Alloys.
Authors: Das J. , Kim K. B. , Baier F. , Loeser W. , Gebert A. , Eckert J.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Fe65.5Cr4Mo4Ga4P12 C5B5.5 BMGs: Sample Preparation, Thermal Stability and Mechanical Properties.
Authors: Stoica M. , Eckert J. , Roth S. , Yavari A. R. , Schultz L.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Synthesis of Mo—Si—B in situ Composites by Mechanical Alloying.
Authors: Yamauchi Akira , Yoshimi Kyosuke , Kurokawa Kazuya , Hanada Shuji
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Metal Phosphite Containing 24‐Ring Channels with 10‐Ring Windows.
Authors: Yang Yali , Li Niu , Song Haibin , Wang Honggen , Chen Wenbin , Xiang Shouhe
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Zr50Sc12O43N50 and Zr3Sc4N8 —Synthesis, Neutron Powder Diffraction and Raman Spectroscopy.
Authors: Martinez Meta N. J. , Schweda E. , Boysen H. , Haug A. , Chasse T. , Hoelzel M.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Syntheses and Structures of Solvated Tetrasodiumtetrachalcogenostannates [Na4(en)4]]SnE4] (en = 1,2‐Diaminoethane; E: Te, Se), and Their Reactions Toward Further Ternary or Quaternary Chalcogenometallates [Mn(en)3]2 [Sn2Te6]×4H2O or [Na10(H2O)34] [Mn4(μ4‐Se)(SnSe4)4].
Authors: Ruzin Eugen , Zimmermann Christian , Hillebrecht Pierre , Dehnen Stefanie
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Two Tungsten Nitride Chlorides: W2NCl8 and W2NCl9.
Authors: Weisser Martina , Tragl Sonja , Meyer H.‐Juergen
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Mixed‐Metal Dawson Sandwich Complexes: Synthesis, Spectroscopic Characterization and Electrochemical Behavior of Na16 [MIICo3(H2O)2 (P2W15O56)2] (M: Mn, Co, Ni, Zn and Cd).
Authors: Ruhlmann Laurent , Costa‐Coquelard Claire , Canny Jacqueline , Thouvenot Rene
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Effect of Cyanato, Azido, Carboxylato, and Carbonato Ligands on the Formation of Cobalt(II) Polyoxometalates: Characterization, Magnetic, and Electrochemical Studies of Multinuclear Cobalt Clusters.
Authors: Lisnard Laurent , Mialane Pierre , Dolbecq Anne , Marrot Jerome , Clemente‐Juan Juan Modesto , Coronado Eugenio , Keita Bineta , de Oliveira Pedro , Nadjo Louis , Secheresse Francis
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
First Chiral Phosphite with a Quaternary Ammonium Fragment: Synthesis and Use in Rh‐Catalyzed Asymmetric Hydrogenation.
Authors: Lyubimov S. E. , Davankov V. A. , Valetskii P. M. , Petrovskii P. V. , Maksimova M. G. , Gavrilov K. N.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Synthesis of Chiral 4‐Substituted 2‐Hydroxypent‐4‐enoic Acid Derivatives via Diastereoselective Ene Reaction Promoted by ZnBr2.
Authors: Kwiatkowski Piotr , Kwiatkowski Jacek , Majer Jakub , Jurczak Janusz
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Rhodium‐Catalyzed Cycloisomerization: Formation of Indoles, Benzofurans, and Enol Lactones.
Authors: Trost Barry M. , McClory Andrew
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Regio‐ and Stereoselective Ring Opening of Epoxides and Aziridines Using Zirconyl Chloride: An Efficient Approach for the Synthesis of β‐Chlorohydrins and β‐Chloroamines.
Authors: Das Biswanath , Krishnaiah Maddeboina , Venkateswarlu Katta
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Improved Dimethylsulfoxonium Methylide Cyclopropanation Procedures, Including a Tandem Oxidation Variant.
Authors: Paxton Richard J. , Taylor Richard J. K.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Oxone‐Mediated Methoxy Thiocyanation of 1,1‐Disubstituted Olefins in Methanol.
Authors: Wu Guaili , Wu Wentao , Li Rui , Shen Yinglin , Wu Longmin
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
A Novel Environmentally Benign Method for the Selective Oxidation of Alcohols to Aldehydes and Ketones.
Authors: Shi Feng , Tse Man Kin , Beller Matthias
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Polycyclic Aromatic Compounds‐Mediated Electrochemical Reduction of Alkyl Mesylates.
Authors: Senboku Hisanori , Takahashi Megumi , Fukuhara Tsuyoshi , Hara Shoji
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Pd‐Catalyzed Cleavage of Benzylic Nitro Bonds: New Opportunities for Asymmetric Synthesis.
Authors: Fessard Thomas C. , Motoyoshi Hajime , Carreira Erick M.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
De novo Synthesis of Troc‐Protected Amines: Intermolecular Rhodium‐Catalyzed C—H Amination with N‐Tosyloxycarbamates.
Authors: Lebel Helene , Huard Kim
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Molecular Structures and Catalytic Activity of Palladium Complexes Derived from Lutidine‐Bridged Bis(benzimidazolin‐2‐ylidene) Ligands.
Authors: Jahnke Mareike C. , Pape Tania , Hahn F. Ekkehardt
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Pyridine‐3‐carboxylic Anhydride (3‐PCA): A Versatile, Practical, and Inexpensive Reagent for Condensation Reaction Between Carboxylic Acids and Alcohols.
Authors: Mukaiyama Teruaki , Funasaka Setsuo
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Synthesis and Selected Transformation of Optically Active Cyclopentenyl Sulfoxides: New Approach to Optically Active Cyclopentenones.
Authors: Midura W. H. , Krysiak J. , Wieczorek M. W. , Filipczak A.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Reactions of “Cage” Dione with Primary Amines — Revision of an Earlier Report.
Authors: Romanski J.
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Solvent‐Free Iodination of Organic Molecules Using the I2/Urea—H2O2 Reagent System.
Authors: Pavlinac Jasminka , Zupan Marko , Stavber Stojan
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.