bluuebunny/crossref_metadata_2025_split huggingface dataset:
Medicinal Organometallic Chemistry: Designing Metal Arene Complexes as Anticancer Agents
Authors: Peacock Anna F. A. , Sadler Peter J. 
Published: August 2008

AbstractThe field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed.
A large‐scale screen for coding variants in SERT/SLC6A4 in autism spectrum disorders
Authors: Sakurai Takeshi , Reichert Jennifer , Hoffman Ellen J. , Cai Guiqing , Jones Hywel B. , Faham Malek , Buxbaum Joseph D. 
Published: August 2008

AbstractIn the current study we explored the hypothesis that rare variants in SLC6A4 contribute to autism susceptibility and to rigid‐compulsive behaviors in autism. We made use of a large number of unrelated cases with autism spectrum disorders (∼350) and controls (∼420) and screened for rare exonic variants in SLC6A4 by a high‐throughput method followed by sequencing. We observed no difference in the frequency of such variants in the two groups, irrespective of how we defined the rare variants. Furthermore, we did not observe an association of rare coding variants in SLC6A4 with rigid‐compulsive traits scores in the cases. These results do not support a significant role for rare coding variants in SLC6A4 in autism spectrum disorders, nor do they support a significant role for SLC6A4 in rigid‐compulsive traits in these disorders.
Putting the Pieces Together: Histone H2B Ubiquitylation Directly Stimulates Histone H3K79 Methylation
Authors: Jeltsch Albert , Rathert Philipp 
Published: August 2008

AbstractEmploying an in vitro reconstitution approach, McGinty et al. studied the mechanism of stimulation of the Dot1‐catalysed histone H3 methylation at Lys79 by histone H2B ubiquitylation at Lys120. To generate nucleosome particles that carry the ubiquitylation at Lys120, they chemically connected three polypeptides—the main parts of histone H3 and ubiquitin expressed in bacteria and a branched synthetic peptide. Using the semisynthetically produced nucleosome substrates and purified Dot1 enzyme, they showed that Dot1 is directly stimulated by the ubiquitylation, thus ruling out the need for further protein factors to mediate the effect.
Comparative Study on the Structural, Optical, and Electrochemical Properties of Bithiophene‐Fused Benzo[c]phospholes
Authors: Matano Yoshihiro , Miyajima Tooru , Fukushima Tatsuya , Kaji Hironori , Kimura Yoshifumi , Imahori Hiroshi 
Published: August 2008

AbstractThree types of bithiophene‐fused benzo[c]phospholes were successfully prepared by TiII‐mediated cyclization of the corresponding dialkynylated bithiophene derivatives as a key step. Each σ3‐phosphorus center of the benzo[c]phosphole subunits was readily transformed into σ4‐phosphorus center by Au coordination or oxygenation. In addition, the bithiophene subunit was functionalized at the α,α′‐carbon atoms by Pd‐catalyzed cross‐coupling reactions with heteroarylmetals and by an SNAr reaction with hexafluorobenzene. The experimentally observed results (NMR spectroscopy, X‐ray analysis, UV/Vis absorption/fluorescence spectroscopy, and cyclic/differential‐pulse voltammetry) have revealed that the structural, optical, and electrochemical properties of the bithiophene‐fused benzo[c]phospholes vary considerably depending on the π‐conjugation modes at the bithiophene subunits and the substituents of the heterocyclopentadiene components. The appropriately ring‐annulated σ3‐P derivatives and σ4‐P‐AuCl complexes were found to emit fluorescence in the orange–red region, and the σ4‐P‐oxo derivatives proved to undergo reversible one‐electron reduction at −1.4 to −1.8 V (vs ferrocene/ferrocenium). These results indicate that the bithiophene‐fused benzo[c]phospholes possess narrow HOMO–LUMO gaps and low‐lying LUMOs, which was confirmed by density functional theory calculations of their model compounds. The time‐of‐flight measurement of an ITO/benzo[c]phosphole/Al device showed that the electron mobility in the P‐oxo derivative is one‐order higher than that in Alq3 at low electric fields. The present study demonstrates that the arene‐fused benzo[c]phosphole skeleton could be a highly promising platform for the construction of a new class of phosphole‐based optoelectrochemical materials.
Kinesin‐5 is not essential for mitotic spindle elongation in Dictyostelium
Authors: Tikhonenko Irina , Nag Dilip K. , Martin Nora , Koonce Michael P. 
Published: August 2008

AbstractThe proper assembly and operation of the mitotic spindle is essential to ensure the accurate segregation of chromosomes and to position the cytokinetic furrow during cell division in eukaryotes. Not only are dynamic microtubules required but also the concerted actions of multiple motor proteins are necessary to effect spindle pole separation, chromosome alignment, chromatid segregation, and spindle elongation. Although a number of motor proteins are known to play a role in mitosis, there remains a limited understanding of their full range of functions and the details by which they interact with other spindle components. The kinesin‐5 (BimC/Eg5) family of motors is largely considered essential to drive spindle pole separation during the initial and latter stages of mitosis. We have deleted the gene encoding the kinesin‐5 member in Dictyostelium, (kif13), and find that, in sharp contrast with results found in vertebrate, fly, and yeast organisms, kif13− cells continue to grow at rates indistinguishable from wild type. Phenotype analysis reveals a slight increase in spindle elongation rates in the absence of Kif13. More importantly, there is a dramatic, premature separation of spindle halves in kif13− cells, suggesting a novel role of this motor in maintaining spindle integrity at the terminal stages of division. Cell Motil. Cytoskeleton 2008. © 2008 Wiley‐Liss, Inc.
Embryological development of Caiman latirostris (Crocodylia: Alligatoridae)
Authors: Iungman Josefina , Piña Carlos I. , Siroski Pablo 
Published: August 2008

AbstractA standard development embryological series is the primary basis to organize information of any embryological study and is also used to determine the age of eggs and embryos in field conditions. In this article, we calibrate developmental series of the broad‐snouted caiman, Caiman latirostris, against an established series for Alligator mississippiensis. Morphometric measures and extend of the opaque‐shell banding were also related to embryo age. In earlier stages, external morphological features alone can account for embryo age, but we suggest that morphometric measurements should be introduced later in the development. Unlike morphologic and morphometric attributes, the opaque patch was not a useful age predictor. As expected, a close correlation between embryonic development of C. latirostris and A. mississippiensis was observed. genesis 46:401–417, 2008. © 2008 Wiley‐Liss, Inc.
Rhodium(III) and Iridium(III) Complexes with Quinolyl‐Functionalized Cp Ligands: Synthesis and Catalytic Hydrogenation Activity
Authors: Kohl Gerald , Pritzkow Hans , Enders Markus 
Published: August 2008

AbstractBis(ethene) complexes of rhodium(I) and iridium(I) with 8‐quinolylcyclopentadienyl ligands (CpQ and CpQ*) were oxidized by a photochemically induced reaction with chlorine‐containing solvents or by treatment with iodine. Upon this oxidation, the quinoline ring rotates and the N donor coordinates to the metal centers. Substitution of the halogenido ligands through acetato groups leads to highly soluble derivatives, in which the acetate moiety acts as a monodentate or bidentate ligand. The new Rh complexes were evaluated as catalysts for the hydrogenation of 1‐hexene. The coordinatively saturated complexes show hydrogenation activity without the necessity of external bases. The catalytic activity is highest for the cationic complex [CpQ*Rh(O2CCH3)]+PF6– (6b), which contains a bidentate acetato ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Rate and Mechanism of the Oxidative Addition of a Silylborane to Pt0 Complexes – Mechanism for the Pt‐Catalyzed Silaboration of 1,3‐Cyclohexadiene
Authors: Durieux Guillaume , Gerdin Martin , Moberg Christina , Jutand Anny 
Published: August 2008

AbstractThe chemical reduction of Pt(acac)2 by DIBALH in the presence of phosphanes, which is used to generate active Pt0 complexes in the Pt‐catalyzed silaboration of cyclohexadiene by 2‐(dimethylphenylsilyl)‐4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane (1) leading to the 1,4‐silaborated product, was mimicked by the electrochemical reduction of Pt(acac)2 in the presence of 2 equiv. of PR3 (R = Ph, nBu). The electrochemical reduction generates free acac anions and neutral Pt0(PR3)2 complexes. The kinetics of the oxidative addition of bromobenzene (used first as a model molecule) and silylborane 1 to the Pt0 complexes was investigated and the rate constants determined. Pt0(PnBu3)2 is much more reactive than Pt0(PPh3)2 towards 1. From the electrochemical study, it emerges that the acac anions released in the reduction of Pt(acac)2 do not coordinate to the Pt0(PR3)2 complexes. Consequently, the rate of the oxidative addition of 1 to Pt0(PR3)2, generated either by the electrochemical reduction or by the chemical reduction by DIBALH, is not affected by the acac anions and a posteriori not by aluminum cations. The oxidative addition and the further step of the catalytic cycle [insertion of the diene into the Pt–B bond of the Si–Pt–B complex generated in the oxidative addition, with formation of the (η3‐allyl)Pt–Si complex] were monitored by NMR spectroscopy. Pt0 and PtII complexes involved in the catalytic cycle were characterized. The oxidative addition is faster when the ligand is PMe2Ph relative to that obtained with PPh3, in agreement with the electrochemical data. No reductive elimination within the (η3‐allyl)Pt–Si complex is observed when the ligand is PMe2Ph, whereas reactions in the presence of PPh3 proceeded to give the final product. As a consequence, PPh3 is a better ligand than PMe2Ph for the catalytic reaction, as observed experimentally. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Influence of cabbage juices on oxidative changes of rapeseed oil and lard
Authors: Tynek Maria , Szukalska Ewa , Bartoszek Agnieszka 
Published: August 2008

AbstractThe influence of white cabbage on oxidative and thermooxidative changes of plant fats (rapeseed oil) and animal fats (lard) was determined by an array of standard tests. The fats were heated at 100 °C for 6 h in a model system mimicking normal cooking conditions in the presence or absence of fresh cabbage juice (FCJ) or sauerkraut juice (SJ). After thermal processing of fats in the presence of cabbage juices, regardless of the kind, the formation of oxidized triacylglycerols (TAG) was decreased by about 40% compared to fats heated alone. Juices also inhibited the formation of TAG dimers and polymers. Such parameters as peroxide value, extinction coefficient at 232 nm (E1%1cm), and losses of polyene fatty acids revealed the protective effect of cabbage juices as well; however, in this case FCJ displayed a much stronger antioxidant effect than SJ. The protection was more visible for lard which contains much lower amounts of natural antioxidants.
Identification of triacylglycerols in the enzymatic transesterification of rapeseed and butter oil
Authors: Svensson Julia , Adlercreutz Patrick 
Published: August 2008

AbstractA blend of rapeseed and butter oil was transesterified using immobilized Thermomyces lanuginosus lipase (Lipozyme® TL IM) as catalyst. The reaction was followed by reversed‐phase HPLC and the triacylglycerol peaks were tentatively identified from their elution times by calculating equivalent carbon numbers. Further identification was made using HPLC‐electrospray tandem mass spectrometry. A few of the triacylglycerols detected were typical combinations of fatty acids originating from rapeseed oil, such as α‐linolenic acid, and short‐chain fatty acids from butter oil. Due to the regioselectivity of the lipase, the transesterification reaction involved mainly fatty acids in the sn‐1 and sn‐3 positions. However, significant changes in the fatty acid composition in the sn‐2 position were detected after 6 h.
Disposable Amperometric Sensors for Thiols with Special Reference to Glutathione
Authors: Bhattacharyay Dipankar , Dutta Kakoli , Banerjee Suchanda , Turner Antony P. F. , Sarkar Priyabrata 
Published: August 2008

AbstractThe antioxidant ‘reduced glutathione’ tripeptide is conventionally called glutathione (GSH). The oxidized form is a sulfur‐sulfur linked compound, known as glutathione disulfide (GSSG). Glutathione is an essential cofactor for antioxidant enzymes; it provides protection also for the mitochondria against endogenous oxygen radicals. The ratio of these two forms can act as a marker for oxidative stress. The majority of the methods available for estimation of both the forms of glutathione are based on colorimetric and electrochemical assays. In this study, electrochemical sensors were developed for the estimation of both GSH and GSSG. Two different types of transducers were used: i) screen‐printed three‐electrode disposable sensor (SPE) containing carbon working electrode, carbon counter electrode and silver/silver chloride reference electrode; ii) three‐electrode disposable system (CDE) consisting of three copper electrodes. 5,5′‐dithiobis(2‐nitrobenzoic acid) (DTNB) was used as detector element for estimation of total reduced thiol content. The enzyme glutathione reductase along with a co‐enzyme reduced nicotinamide adenine dinucleotide phosphate was used to estimate GSSG. By combining the two methods GSH can also be estimated. The detector elements were immobilized on the working electrodes of the sensors by bulk polymerization of acrylamide. The responses were observed amperometrically. The detection limit for thiol (GSH) was less than 0.6 ppm when DTNB was used, whereas for GSSG it was less than 0.1 ppm.
Selective Cosmetic Mercury Analysis Using a Silver Ink Screen‐Printed Electrode with Potassium Iodide Solution
Authors: Chiu Mei‐Hsin , Zen Jyh‐Myng , Kumar Annamalai Senthil , Vasu Dhananjayan , Shih Ying 
Published: August 2008

AbstractA new method for selective determination of trace mercury has been demonstrated by linear scan voltammetry using silver ink screen printed electrode (AgSPE) in presence of potassium iodide (KI) dissolved 0.05 M H2SO4 solution. At AgSPE, iodide oxidation peak current signal found to be systematically decreased (inhibitory current anodic peak current signal, i$\rm{ {_{pa}^{in}}}$) with increase in the Hg concentrations, [Hg]. This observation is further utilized for construction of new Hg electroanalytical assays in this work. On the AgSPE, Hg inhibitory detection potential found at 0 V vs. Ag/AgCl, which is 720 mV lower than that of unmodified SPE system. Under optimal experimental conditions, i$\rm{ {_{pa}^{in}}}$ signals were linearly increased against [Hg] in the window of 500–4500 ppb (40 μM KI) with a correlation coefficient (r) of 0.9988. The limit of detection (LOD) and limit of quantification (LOQ) were 98 and 318 ppb, respectively. This approach was further utilized to analyze hidden Hg in the cosmetic samples. Real sample assays were consistent with that of result obtained from ICP‐OES, which confirm the applicability of the proposed method for practical applications.
Chromosome aberrations in peripheral blood lymphocytes of high‐risk HPV‐infected women with HGSIL
Authors: Álvarez‐Rosero Rosa E. , Rodríguez‐Argote Jannet , Arboleda‐Moreno Yexania Y. , Muñoz‐Benítez Sulma L. , Sierra‐Torres Carlos H. 
Published: August 2008

AbstractGenomic instability is one of the main characteristics of malignant tumors, including HPV‐induced cervical cancer. The aim of this study was to explore the use of assessing chromosome aberrations (CA) in peripheral blood lymphocytes as a biomarker for genomic instability in high‐risk HPV‐infected women with high‐grade squamous intraepithelial lesions (HGSIL). A total of 120 women were recruited for this study, following cytology/colposcopy evaluation and HPV DNA detection. The study groups consisted of 30 HPV(+) women with histologically confirmed cervical intraepithelial neoplasia grade 2/3 and 30 HPV(+) women with carcinoma in situ (CIS). Two control groups, including 30 women HPV(−) and 30 women HPV(+), were recruited among women who were reported as cytology negative. Lymphocyte cell cultures were established for 52 hr, and 100 complete metaphase cells were evaluated per subject for CA analysis. The results show that women with CIS had significantly higher frequencies of both aneuploidy (0.67 ± 0.20 vs. 0.14 ± 0.08, P = 0.020) and tetraploidy (0.88 ± 0.23 vs. 0.17 ± 0.08, P = 0.013) in comparison with HPV(−) controls. These findings suggest the usefulness of peripheral blood lymphocytes to detect genomic instability associated with HPV‐induced HGSIL. Environ. Mol. Mutagen., 2008. © 2008 Wiley‐Liss, Inc.
Linear retention indices in gas chromatographic analysis: a review
Authors: Zellner Barbara d'Acampora , Bicchi Carlo , Dugo Paola , Rubiolo Patrizia , Dugo Giovanni , Mondello Luigi 
Published: August 2008

AbstractThe main purpose of any chromatographic analysis is to resolve mixtures of compounds into less complex mixtures or ultimately into pure components. In addition to this function, the chromatographic system can provide retention data which serve as complementary information for the positive identification of resolved components. The need to express gas chromatographic retention data in a standardized system has long been recognized and retention index values presented to be a valuable parameter. Those values are mainly calculated by applying the equations proposed by Kováts, for isothermal analysis, and van den Dool and Kratz, for programmed gas chromatographic runs. In general, these indices denote the retention behaviour of the compounds of interest according to a uniform scale determined by a series of closely related standard substances. The use of retention indices in the flavour and fragrance field is well‐documented, and they are widely applied for the comparison of results between laboratories, as well as to characterize stationary phases. Copyright © 2008 John Wiley & Sons, Ltd.
Efficient and robust algorithms for solution of the adjoint compressible Navier–Stokes equations with applications
Authors: Dwight Richard P. , Brezillon Joël 
Published: August 2008

AbstractThe complete discrete adjoint equations for an unstructured finite volume compressible Navier–Stokes solver are discussed with respect to the memory and time efficient evaluation of their residuals, and their solution. It is seen that application of existing iteration methods for the non‐linear equation—suitably adjointed—has a property of guaranteed convergence provided that the non‐linear iteration is well behaved. For situations where this is not the case, in particular for strongly separated flows, a stabilization technique based on the Recursive Projection Method is developed. This method additionally provides the dominant eigenmodes of the problem, allowing identification of flow regions that are unstable under the basic iteration. These are found to be regions of separated flow. Finally, an adjoint‐based optimization with 96 design variables is performed on a wing–body configuration. The initial flow has large regions of separation, which are significantly diminished in the optimized configuration. Copyright © 2008 John Wiley & Sons, Ltd.
Influence of Potsdam sandstone on the trace element signatures of some 19th‐century American and Canadian glass: Redwood, Redford, Mallorytown, and Como–Hudson
Authors: Owen J. Victor , Greenough John D. 
Published: August 2008

AbstractPotsdam sandstone from quarries and outcrops near 19th‐century glassworks sites in Redwood, NY, and Saranac, NY, Mallorytown, ON, and Como and Hudson, QC, commonly contains _97% silica, so in terms of its purity can compete with other historical producers of silica sand (e.g., Cheshire quartzite, MA; southern New Jersey sand). Exploratory analysis of trace element data using multidimensional scaling (MDS) shows that geographically distinct sources of Potsdam sandstone can be distinguished from one another and from competing sources of silica sand, particularly in terms of high field strength elements (e.g., Nb, Y, Ti, Zr), the rare earth elements, and radioactive elements (U, Th), and this geochemical signature is carried through to the glass it was used to manufacture. Other trace elements (e.g., Ba, Sr, Rb) are concentrated in various batch ingredients (e.g., limestone, alkali fluxes). The Hf/Nb, La/Ce, Nb/Th, and La/Zr ratios for each type of glass and nearby Potsdam sandstone sources cluster together in distinct fields on MDS plots. These data confirm the use of Potsdam sandstone in these important historical glassworks, and show that except for material sampled from neighboring communities (Mallorytown and Redwood), trace elements can be used to identify specific sources of silica historically used by the glassmaking industry. © 2008 Wiley Periodicals, Inc.
Long‐term population‐based risks of breast cancer after childhood cancer
Authors: Reulen Raoul C. , Taylor Aliki J. , Winter David L. , Stiller Charles A. , Frobisher Clare , Lancashire Emma R. , McClanahan Fabienne M. , Sugden Elaine M. , Hawkins Mike M. ,   on behalf of the British Childhood Cancer Survivor Study
Published: August 2008

AbstractPrevious studies have reported substantially increased risks of breast cancer among survivors of childhood cancer at 10–20 years posttreatment. Whether these excess risks are sustained beyond 40 years of age when general population incidence of breast cancer begins its steep increase is largely unknown. We quantified the risk of breast cancer in adult female survivors with considerably more survivors followed‐up beyond 40 years of age than previously available. Standardized Incidence Ratios (SIR), Excess Absolute Risks (EAR), and cumulative incidence were calculated within a population‐based cohort of 8,093 female survivors of childhood cancer. Poisson regression models were used to model SIRs and EARs in a multivariable setting. Eighty‐one survivors developed a primary breast cancer, where 37.5 were expected (SIR= 2.2, 95% CI: 1.7–2.7). SIRs decreased significantly with increasing attained age (ptrend < 0.001) to an SIR of 0.9 (95% CI: 0.5–1.8) at ages beyond 50 years; EARs increased significantly to about 40 years of age (ptrend < 0.001) but then plateau. Between 30 and 49 years of age survivors experienced approximately 1 extra breast cancer per 1,000 survivors per year. Overall, 3% developed breast cancer by the age of 50. The substantially increased relative risks of breast cancer observed at 10–20 years postdiagnosis are not sustained into ages at which the risk of breast cancer in the general population becomes substantial. Among women who survived to an age of at least 50 years there is currently no evidence of an increased risk of breast cancer. © 2008 Wiley‐Liss, Inc.