bluuebunny/crossref_metadata_2025 huggingface dataset:
Oceanic and atmospheric patterns during spawning periods prior to extreme catches of the Brazilian sardine (Sardinella brasiliensis) in the southwest Atlantic
Authors: Cachanhuk Soares Helena , Ponzi Pezzi Luciano , Marcolino Gherardi Douglas Francisco , Tavares Paes Eduardo
Published: September 2011

Relative maxima and minima of landings of Brazilian sardine captured in the Southeast Brazil Bight (SBB) were compared with oceanic and atmospheric composites relative to the spawning period in December and January, prior to these landings. Atmospheric and oceanic variables such as wind stress, Ekman transport, mixing index, sea surface temperature (SST), precipitation, outgoing long wave radiation and geopotential height were analyzed, revealing distinct climatological patterns in the SBB for these extreme catches that have not been described before. The system could be characterized by cooler SST composite anomaly (SSTA) along the SBB as a response to increased cloud cover and reduced incidence of short-wave radiation, predominating one year before the Brazilian sardine catch maxima. This system can take on a different configuration in which positive SSTA condition in the SBB is associated with a less intense South Atlantic Convergence Zone displaced southwards one year before the period of minimum catch. Our results indicate that the spatial structure of the spawning habitat is influenced by specific ocean-atmosphere interactions rather than simply resulting from the choice of a stable environment. This climatic constraint strongly affects the interannual variability of the Brazilian sardine production.
Instruments et pratique scientifique : l’évolution des choix et des pratiques dans le cabinet de physique des enfants de France à Versailles d’après les inventaires des Menus Plaisirs (1758-1765)
Authors: Mormiche Pascale
Published: September 2011

Cette communication concerne l’enseignement scientifique des princes et la composition de cabinet d’instruments scientifiques. Le premier cabinet constitué à Versailles est celui des enfants de France établi sous le contrôle des Menus Plaisirs. À partir de 1758, il se compose d’instruments choisis parmi les 345 décrits dans le catalogue de l’abbé Nollet en 1738 dans son Programme ou Idée générale d’un cours de physique expérimentale. En 1762 sont déjà achetés plus de 180 objets scientifiques, instruments, matériaux et meubles qu’enrichissent les achats successifs qui se poursuivront en 1765, date à laquelle existe un autre inventaire. Aussi étonnant que cela paraisse, ces deux inventaires n’ont jamais été comparés, ni mis en perspective avec la liste faite lors des séquestres révolutionnaires.Ainsi ces deux inventaires successifs pour ce rare cabinet princier permettent de préciser la culture scientifique des princes grâce au choix minutieux d’objets commandés à l’abbé Nollet par l’équipe préceptorale qui enseigne aux princes. La politique d’acquisition de ces instruments donne des indications sur les pratiques scientifiques des princes. L’électricité fut-elle plus favorisée que la mécanique ou les fluides ? Quelle fut la place de l’observation de l’infiniment grand, de l’infiniment petit ? S’est-on procuré des instruments auprès d’autres constructeurs ? On peut comparer utilement avec un cabinet dont on connaît le rare inventaire d’achat, celui de Mme Du Châtelet et Voltaire possédant également des instruments Nollet. L’analyse de ces inventaires va bien au-delà du simple choix d’instruments pour constituer le cabinet de physique des enfants de France. Il s’agit de relier les instruments avec la pratique pédagogique des princes en montrant la création d’une « discipline scolaire » enseignée aux princes, alors que se déroulent des démonstrations publiques à la cour. Peut-on distinguer ainsi un cabinet d’éducation, un cabinet d’expérimentation, une collection d’instruments ?Cette communication part de sources historiques précises afin d’approfondir la connaissance de l’éducation scientifique du duc de Berry (futur Louis XVI) et de ses frères, restée souvent générale. Elle s’inscrit dans le cadre de l’épistémologie des sciences et des recherches pédagogiques sur la naissance de la culture scientifique qui eut lieu à Versailles. Elle prolonge les travaux de recherche actuels sur les cabinets de curiosité qui s’interrogent sur la pratique scientifique du xviiie siècle.
Molecular Mechanisms of Trastuzumab Resistance in HER2 Overexpressing Breast Cancer
Authors: Fiszman Gabriel L. , Jasnis María A.
Published: September 2011

The epidermal growth factor receptor 2 (HER2) is a tyrosine kinase overexpressed in nearly 20% to 25% of invasive breast cancers. Trastuzumab is a humanized monoclonal antibody that targets HER2. The majority of patients with metastatic breast cancer initially respond to trastuzumab, however, within 1 year of treatment disease progresses. Several molecular mechanisms have been described as contributing to the development of trastuzumab resistance. They could be grouped as impaired access of trastuzumab to HER2, upregulation of HER2 downstream signaling pathways, signaling of alternative pathways, and impaired immune antitumor mechanisms. However, since many of them have overlapping effects, it would be of great clinical impact to identify the principal signaling pathways involved in drug resistance. Significant efforts are being applied to find other therapeutic modalities besides trastuzumab treatment to be used alone or in combination with current modalities.
MAMAP – a new spectrometer system for column-averaged methane and carbon dioxide observations from aircraft: retrieval algorithm and first inversions for point source emission rates
Authors: Krings T. , Gerilowski K. , Buchwitz M. , Reuter M. , Tretner A. , Erzinger J. , Heinze D. , Pflüger U. , Burrows J. P. , Bovensmann H.
Published: September 2011

Abstract. MAMAP is an airborne passive remote sensing instrument designed to measure the dry columns of methane (CH4) and carbon dioxide (CO2). The MAMAP instrument comprises two optical grating spectrometers: the first observing in the short wave infrared band (SWIR) at 1590–1690 nm to measure CO2 and CH4 absorptions, and the second in the near infrared (NIR) at 757–768 nm to measure O2 absorptions for reference/normalisation purposes. MAMAP can be operated in both nadir and zenith geometry during the flight. Mounted on an aeroplane, MAMAP surveys areas on regional to local scales with a ground pixel resolution of approximately 29 m × 33 m for a typical aircraft altitude of 1250 m and a velocity of 200 km h−1. The retrieval precision of the measured column relative to background is typically ≲1% (1σ). MAMAP measurements are valuable to close the gap between satellite data, having global coverage but with a rather coarse resolution, on the one hand, and highly accurate in situ measurements with sparse coverage on the other hand. In July 2007, test flights were performed over two coal-fired power plants operated by Vattenfall Europe Generation AG: Jänschwalde (27.4 Mt CO2 yr−1) and Schwarze Pumpe (11.9 Mt CO2 yr−1), about 100 km southeast of Berlin, Germany. By using two different inversion approaches, one based on an optimal estimation scheme to fit Gaussian plume models from multiple sources to the data, and another using a simple Gaussian integral method, the emission rates can be determined and compared with emissions reported by Vattenfall Europe. An extensive error analysis for the retrieval's dry column results (XCO2 and XCH4) and for the two inversion methods has been performed. Both methods – the Gaussian plume model fit and the Gaussian integral method – are capable of deriving estimates for strong point source emission rates that are within ±10% of the reported values, given appropriate flight patterns and detailed knowledge of wind conditions.
Temporal variability of live (stained) benthic foraminiferal faunas in a river-dominated shelf – faunal response to rapid changes of the river influence (Rhône prodelta, NW Mediterranean)
Authors: Goineau A. , Fontanier C. , Jorissen F. , Buscail R. , Kerhervé P. , Cathalot C. , Pruski A. M. , Bourgeois S. , Metzger E. , Legrand E. , Rabouille C.
Published: September 2011

Abstract. In the context of the French research project CHACCRA (Climate and Human-induced Alterations in Carbon Cycling at the River–seA connection), living (rose Bengal-stained) benthic foraminifera were investigated at two stations (24 and 67 m depth) in the Rhône prodelta (NW Mediterranean, Gulf of Lions). The aim of this study was to precise the response of benthic foraminiferal faunas to temporal changes of the Rhône River inputs (e.g. organic and terrigeneous material). Each site was sampled in April 2007, September 2007, May 2008 and December 2008, permitting to observe foraminiferal faunas of the 63–150 and >150 μm size fractions under a wide range of environmental conditions. Obvious variations in foraminiferal faunal composition were observed during the four investigated periods at the shallowest Station A located in the close vicinity of the Rhône River mouth. Different colonisation stages were observed after major Rhône River flood events, foraminiferal faunas responding with an opportunistic strategy few days to weeks after the creation of a peculiar sedimentary environment (Leptohalysis scottii, May 2008) or high amounts of organic matter supplied by a river flood (Ammonia tepida, December 2008). Under more stable conditions, relatively diverse and equilibrated faunas grew in the sediments. Species benefited from noticeable input of riverine phytodetritus to the sediment during spring bloom conditions (April 2007; e.g. Bolivina dilatata, Nonionella stella, Stainforthia fusiformis), or high amounts of still bio-available organic matter under more oligotrophic conditions (September 2007; e.g. Ammonia tepida, Psammosphaera fusca). The reduced influence of the Rhône River input at the farther Station N led to less contrasted environmental conditions during the four sampling periods, and so to less obvious variations in foraminiferal faunal composition. During reduced riverine influence (i.e. low Rhône discharge), species able to feed on fresh phytodetritus (e.g. Clavulina cylindrica, Hopkinsina atlantica, Nonionella iridea and Nonionella turgida) benefited from eutrophic conditions of the spring bloom (April 2007, May 2008). Conversely, the occurrence of Nouria polymorphinoides under oligotrophic conditions (September 2007, December 2008) was indicative of a benthic environment potentially disturbed by bottom currents. This study put into evidence the extremely rapid response of benthic foraminiferal faunas to strong variations in environmental conditions, especially close to the river mouth (Station A), response noticeably reduced farther from the mouth (Station N) due to a weaker impact of riverine input.
Evaluation of Proteomics-Identified CCL18 and CXCL1 as Circulating Tumor Markers for Differential Diagnosis between Ovarian Carcinomas and Benign Pelvic Masses
Authors: Wang Qi , Li Danrong , Zhang Wei , Tang Bujian , Li Qingdi Quentin , Li Li
Published: September 2011

A lack of sensitive and specific tumor markers for early diagnosis and treatment is a major cause for the high mortality rate of ovarian cancer. The purpose of this study was to identify potential proteomics-based biomarkers useful for the differential diagnosis between ovarian cancer and benign pelvic masses. Serum samples from 41 patients with ovarian cancer, 32 patients with benign pelvic masses, and 41 healthy female blood donors were examined, and proteomic profiling of the samples was assessed by surface-enhanced laser desorption/ionization time-of-flight (SELDI-TOF) mass spectroscopy (MS). A confirmatory study was also conducted with serum specimens from 58 patients with ovarian carcinoma, 37 patients with benign pelvic masses, and 48 healthy women. A classification tree was established using Biomarker Pattern Software. Six differentially expressed proteins (APP, CA 125, CCL18, CXCL1, IL-8, and ITIH4) were separated by high-performance liquid chromatography and identified by matrix-assisted laser desorption/ionization (MALDI)-MS/MS and database searches. Two of the proteins overexpressed in ovarian cancer patients, chemokine CC2 motif ligand 18 (CCL18) and chemokine CXC motif ligand 1 (CXCL1), were automatically selected in a multivariate predictive model. These two protein biomarkers were then validated and evaluated by enzyme-linked immunosorbent assay (ELISA) in 535 serum specimens (130 ovarian cancer, 64 benign ovarian masses, 36 lung cancer, 60 gastric cancer, 55 nasopharyngeal carcinoma, 48 hepatocellular carcinoma, and 142 healthy women). The combined use of CCL18 and CXCL1 as biomarkers for ovarian cancer had a sensitivity of 92% and a specificity of 97%. The multivariate ELISA analysis of the two putative markers in combination with CA 125 resulted in a sensitivity of 99% for healthy women and 94% for benign pelvic masses, and a specificity of 92% for both groups; these values were significantly higher than those obtained with CA 125 alone (P<0.05). We conclude that serum CCL18 and CXCL1 are potentially useful as novel circulating tumor markers for the differential diagnosis between ovarian cancer and benign ovarian masses.
Estratégias de Marketing Digital na Era da Busca
Authors: Okada Sionara Ioco , Souza Eliane Moreira Sá de
Published: September 2011

A evoluo das tecnologias de comunicao e informao TICs inauguram uma era de crescimento e disseminao exponencial de contedo relevante. Com a expanso da ubiqidade on-line, o crescimento e a facilidade de acesso web mvel, via dispositivos portteis, a busca popularizou-se e os mecanismos de busca cresceram e se sofisticaram. O presente artigo tem como foco fazer uma atualizao das publicaes mais recentes das Estratgias de Marketing Digital, ampliando a visibilidade de conceitos e tendncias importantes: i) evoluo da web 2.0 para web semntica ii) Marketing de busca, Estratgias SEM e SEO iii) mbile tagging, QR codes e Realidade Aumentada. Trata-se de uma pesquisa exploratria e uma investigao secundria, sobretudo bibliogrfica, privilegiando publicaes em sites especializados, notadamente no perodo de 1995 a 2010. Algumas inovaes tecnolgicas se tornaram marcantes e se transformaram em fortes tendncias, impactando os profissionais de marketing e de Tecnologia de Informao (TI). A migrao do consumo para a web, as facilidades dos mecanismos de buscas por melhores produtos e referncias e o aumento do consumo em tempo real, assumem-se como tendncias irreversveis, que exigem das organizaes estratgias mercadolgicas eficientes. Assim, torna-se imperativo gerenciar a comunicao empresarial na Era da busca exigindo uma postura de atualizao permanente e estratgias de marketing dirigidas e sustentveis. DOI: 10.5585/remark.v10i1.2199
Preparation of HCV NS3 and NS5B Proteins to Support Small‐Molecule Drug Discovery
Authors: Hung Magdeleine , Wang Ruth , Liu Xiaohong
Published: September 2011

Production of high‐quality, well‐characterized recombinant proteins facilitates screening of compound libraries. The protocols detailed in this unit are used to purify three recombinant enzymes that are widely used in HCV research: the HCV NS3 protease domain, the helicase domain as an NS3+NS4A complex, and the NS5B RNA‐dependent RNA polymerase. The active enzymes are purified to homogeneity by two‐column chromatography to support a screening program for HCV inhibitors. Curr. Protoc. Pharmacol. 54:13B.6.1‐13B.6.18. © 2011 by John Wiley & Sons, Inc.
Immunoblotting and Immunodetection
Authors: Gallagher Sean , Winston (tank transfer systems) Scott E. , Fuller (tank transfer systems) Steven A. , Hurrell (tank transfer systems; reversible staining of prote John G.R.
Published: September 2011

Immunoblotting (western blotting) is used to identify specific antigens recognized by polyclonal or monoclonal antibodies. This unit provides protocols for all steps, starting with solubilization of the protein samples, usually by means of SDS and reducing agents. Following solubilization, the material is separated by SDS‐PAGE and the antigens are electrophoretically transferred to a membrane, a process that can be monitored by reversible staining with Ponceau S. The transferred proteins are bound to the surface of the membrane, providing access to immunodetection reagents. After nonspecific binding sites are blocked, the membrane is probed with the primary antibody and washed. The antibody‐antigen complexes are tagged with horseradish peroxidase or alkaline phosphatase coupled to a secondary anti‐IgG antibody, and detected using appropriate chromogenic or luminescent substrates. Finally, membranes may be stripped and reprobed. Curr. Protoc. Cell Biol. 52:6.2.1‐6.2.28. © 2011 by John Wiley & Sons, Inc.
Transfection by Electroporation
Authors: Potter Huntington , Heller Richard
Published: September 2011

Electroporation—the use of high‐voltage electric shocks to introduce DNA into cells—can be used with most cell types, yields a high frequency of both stable transformation and transient gene expression, and, because it requires fewer steps, can be easier than alternate techniques. This unit describes electroporation of mammalian cells, including ES cells for the preparation of knock‐out, knock‐in, and transgenic mice. Protocols are described for the use of electroporation in vivo to perform gene therapy for cancer therapy and DNA vaccination. Also described are modifications for preparation and transfection of plant protoplasts. Curr. Protoc. Cell Biol. 52:20.5.1‐20.5.10. © 2011 by John Wiley & Sons, Inc.
White monkey syndrome and presumptive copper deficiency in wild savannah baboons
Authors: Markham A. Catherine , Gesquiere Laurence R. , Bellenger Jean‐Philippe , Alberts Susan C. , Altmann Jeanne
Published: September 2011

In immature wild savannah baboons (Papio cynocephalus), we observed symptoms consistent with copper (Cu) deficiency and, more specifically, with a disorder referred to as white monkey syndrome (WMS) in laboratory primates. The objectives of this study were to characterize this pathology, and test three hypotheses that (1) Cu deficiency may have been induced by zinc (Zn) toxicity, (2) it may have been induced by molybdenum (Mo) toxicity, and (3) cumulative rainfall during the perinatal period and particularly during gestation is an ecological factor distinguishing infants afflicted with WMS from non‐WMS infants. During 2001–2009, we observed 22 instances of WMS out of a total 377 live births in the study population. Visible symptoms exhibited by WMS infants included whitening of the animal's fur and/or impaired mobility characterized by an apparent “stiffening” of the hindlimbs. Occurrence of WMS did not vary significantly by gender. However, among individuals that survived at least 180 days, WMS males had a significantly lower survivorship probability than non‐WMS males. Zn/Cu ratios assessed from hair samples of adult female baboons were higher in females who had produced at least one WMS offspring relative to females who had not had a WMS offspring. This was true even when the hair sample was collected long after the birth of the female's afflicted infant. We consider this potentially indicative of a robust tendency for low Cu levels induced by elevated Zn intake in some individuals. No significant differences of Mo/Cu ratios were observed. Cumulative rainfall during gestation (∼179 days) was 50% lower for WMS infants relative to non‐WMS infants. In contrast, rainfall for the two classes of infants did not differ in the 180 days before conception or in the 180 days following birth. This finding highlights the importance of prenatal ecological conditions in healthy fetal development with regard to WMS. Am. J. Primatol. 73:1160–1168, 2011. © 2011 Wiley Periodicals, Inc.
Male dispersal in a provisioned multilevel group ofRhinopithecus roxellanain Shennongjia Nature Reserve, China
Authors: Yao Hui , Liu Xuecong , Stanford Craig , Yang Jingyuan , Huang Tianpeng , Wu Feng , Li Yiming
Published: September 2011

Most Old World monkeys show male‐biased dispersal. We present the first systematic data on male dispersal in a provisioned multilevel group ofRhinopithecus roxellana, based on 4.5 years of field observations in Shennongjia National Nature Reserve, China. We evaluated both ultimate (inbreeding avoidance and male mating competition) and proximate (food availability and predation risk) factors influencing male dispersal. The focal group contained 34–53 individuals, in 3–4 one‐male units (OMUs) and 1 all‐male unit (AMU). We observed 37 dispersal events involving 10 of 11 adults, 7 of 8 subadults, and 7 of 15 juveniles. Most interunit transfers within the focal group occurred around the months of mating season. Adult males competed for the leader positions of OMUs mainly through aggressive takeovers, and young males transferred from the OMUs to the AMU at the median age of 41 months, forced out by leader males. No young males older than 4 years remained in natal or non‐natal OMUs. The male mating competition hypothesis was supported. The young males emigrated voluntarily from the focal group at the average age of 58.6 months, and no young emigrating male was observed to return, suggesting inbreeding avoidance also played a role in the dispersal of young males. Most emigration/immigration events were parallel dispersal and occurred during intergroup encounters, suggesting increased predation risk during the dispersal period. Males were more likely to emigrate/immigrate during the months when preferred foods were most available. We compared the dispersal patterns inR. roxellanawith those in gelada baboons and hamadryas baboons, both living in multilevel societies. Similar toR. roxellana, young male geladas disperse at puberty, but they may return and breed in their natal groups. Males in hamadryas also disperse, but much less commonly than inR. roxellana. Provisioning may have influenced results, and confirming studies on unprovisioned groups would be valuable. Am. J. Primatol. 73:1280–1288, 2011. © 2011 Wiley Periodicals, Inc.
Biosorption of Reactive Red 198 from an aqueous solution using Acalypha indica
Authors: Praveena N. , Saravanan P. , Dharmendira Kumar M. , Nagendra Gandhi N. , Renganathan S.
Published: September 2011

The biosorption of reactive red 198 dye using Acalypha indica was investigated in a batch experimental process. The equilibrium dye uptake capacity of A. indica was determined with the influence of various environmental parameters such as sorbent dosage (0.02–0.1 g 100 mL−1), initial pH (1–6), and initial dye concentration (30–110 mg L−1). Batch experiments were carried out for biosorption kinetics and isotherm studies. The results showed that dye uptake capacity was found to increase with decreases in biosorbent dosage. Equilibrium uptake capacity was found to be more at pH value of 2, when compared with all other pH values studied. The equilibrium data was analyzed with the use of Freundlich and Langmuir adsorption isotherm models. The equilibrium data was found to be fitted very well with the Freundlich isotherm model when compared with the Langmuir isotherm model. The kinetic data was analyzed using pseudo‐first order and pseudo‐second order kinetic models. From the result, it was observed that the kinetic data was found to fit well with the pseudo‐second order kinetic model. The surface morphology of the leaves of the A. indica biomass was exemplified by scanning electron microscope. Fourier transform infrared analysis was employed to confirm the existence of an amine group in the A. indica. © 2011 Curtin University of Technology and John Wiley & Sons, Ltd.
Characterizations of UV‐curable montmorillonite/epoxy nanocomposites prepared by a hybrid of chemical dispersion and planetary mechanical milling process
Authors: Huang Heh‐Chang , Huang Shu‐Ping , Hsieh Tsung‐Eong , Chen Chin‐Hsin
Published: September 2011

Ammonium salt, [2‐(methacyloyloxy)ethyl] trimethylammonium methyl sulfate (MAOTMA), was adopted to modify montmorillonite (MMT) via the cationic exchange process in an acidic environment and a successful enlargement of MMT lamellar spacing from 1.18 to 1.39 nm was identified by x‐ray diffraction and Fourier‐transform infrared spectroscopy. Accordingly, UV‐curable epoxy nanocomposite resins containing various amounts of MAOTMA‐modified MMT were prepared with the aid of a planetary mechanical milling process. Transmission electron microscopy revealed a uniform dispersion of exfoliated MMT lamella in epoxy matrix, leading to the distinct improvements on thermal stability and thermal expansion property of nanocomposite samples. Calcium (Ca) test indicated that the good dispersion of MMT fillers in polymer effectively suppresses the moisture permeation in sample matrix. More than twofold increment on retention time of 5% Ca hydrolysis and 20% improvement on the permeation kinetic parameters were observed in the nanocomposite sample containing 8 wt % MMT in comparison with the pristine epoxy sample. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Th2 and regulatory immune reactions contribute to IgG4 production and the initiation of Mikulicz disease
Authors: Tanaka Akihiko , Moriyama Masafumi , Nakashima Hitoshi , Miyake Katsuhisa , Hayashida Jun‐Nosuke , Maehara Takashi , Shinozaki Shouichi , Kubo Yoshiaki , Nakamura Seiji
Published: September 2011

Objective

Mikulicz disease has been considered to be a subtype of Sjögren's syndrome (SS). However, recent studies have suggested that Mikulicz disease is an IgG4‐related disease and is distinguishable from SS. In addition, it has been reported that both interleukin‐4 (IL‐4) and IL‐10 induce IgG4 production and inhibit IgE. This study was undertaken to examine the expression of these cytokines in patients with Mikulicz disease and patients with SS.

Methods

Labial salivary gland (LSG) sections from 15 patients with Mikulicz disease and 18 patients with SS were examined for subsets of the infiltrating lymphocytes, expression patterns of messenger RNA (mRNA) for cytokines/chemokines, and relationships between the IgG4:IgG ratio and the expression of mRNA for IL‐4 or IL‐10.

Results

Immunohistochemical analysis showed lymphocyte infiltration of various subsets in the LSGs of SS patients, and the selective infiltration of IgG4‐positive plasma cells and Treg cells in the LSGs of Mikulicz disease patients. The levels of mRNA for both Th1 and Th2 cytokines and chemokines in LSGs from patients with SS were significantly higher than in controls, while the expression of both Th2 and Treg cells was significantly higher in the patients with Mikulicz disease than in controls. Furthermore, the expression of IL‐4 or IL‐10 in the LSGs was correlated with the IgG4:IgG ratio.

Conclusion

These results suggest that the pathogenesis of Mikulicz disease is different from that of SS. Mikulicz disease is a unique inflammatory disorder characterized by Th2 and regulatory immune reactions that might play key roles in IgG4 production.
Structure and properties of camptothecin derivatives, their protonated forms, and model interaction with the topoisomerase I–DNA complex
Authors: Ivanova Bojidarka , Spiteller Michael
Published: September 2011

The structure and properties of the 11 Camptothecin derivatives (CPTs) and their different mono‐, di‐, and triprotonated forms, depending on the number of proton accepting centers in the molecules are studied both theoretically and experimentally by quantum chemical approaches, electronic absorption, and CD spectroscopy. The study of the protonated forms of the CPTs and search of the electron‐withdrawing groups is crucial of the water‐solubility of the novel medications. Thus, the model interaction of the different protonated molecular species with the Topoisomerase I–DNA complex are elucidated and discussed with a view to understand the mode of binding of the CPTs depending on the type of the substituents and pH of the medium. © 2011 Wiley Periodicals, Inc. Biopolymers 97: 134–144, 2012.
Determination of therapeutic oligonucleotides using capillary gel electrophoresis
Authors: Chen Buyun , Bartlett Michael G.
Published: September 2011

Oligonucleotides have developed into highly versatile and selective therapeutics over the past 20 years. More than five discrete mechanisms of action have been reported and more than 10 different chemical modifications have been used to extend their in vivo half‐life and reduce their toxicity. Capillary gel electrophoresis (CGE) has been used extensively for the quantitative analysis of oligonucleotide therapeutics in both preclinical and clinical studies since the 1990s. The success of CGE is based on its extraordinary resolving power, which allows for the simultaneous determination of the parent drug and its metabolites. More recently, capillary gel electrophoresis has seen renewed interest with the emergence of replaceable gels with single‐base resolving power and new capillary electrophoresis–mass spectrometry interfaces. This review discusses the bioanalysis of therapeutic oligonucleotides showing the evolution of the field over the past two decades leading to the current new approaches. Included in this review are topics such as different gel types, sample introduction modes, sample extraction procedures, separation conditions and detection methods used in CGE, along with discussions of the successes and limitations associated with each. Copyright © 2011 John Wiley & Sons, Ltd.
Structure/Redox potential relationship of simple organic compounds as potential precursors of dyes for laccase‐mediated transformation
Authors: Polak Jolanta , Jarosz‐Wilkolazka Anna
Published: September 2011

The aim of this study was to examine the ability of an extracellular fungal laccase (LAC) to form colored products from simple non‐colored organic precursors. Thirty different phenolic and non‐phenolic precursors (o‐, m‐, and p‐methoxy‐, hydroxy‐, sulfonic‐, and amino‐substituted) were tested as single and coupled substrates in a LAC‐catalyzed oxidation. The findings show that LAC catalyzes the formation of colored products (from yellow/brown to red and blue) by oxidation of single substrates that are benzene derivatives containing at least two substituents comprised of amino, hydroxy, and methoxy groups. All precursors were tested by cyclic voltammetry and the correlation between their structure and redox potential, and the possibility of their transformation into colored products by fungal LAC was found. Colored products were yielded from single substrates possessing a value of the oxidation peak (Eo) lower than 1,150 mV vs. normal hydrogen electrode (NHE). Substrates with an oxidation peak higher than 1,150 mV vs. NHE were transformed by LAC into colored compounds only in the presence of an additional precursor characterized by a low value of Eo and the presence of reactive substituents such as methoxy, hydroxy, and amino groups. Therefore, additional hydroxylation, methoxylation, and amination of phenolic and non‐phenolic substrates may represent a strategy to increase the range of these compounds as potential dyes precursors. © 2011 American Institute of Chemical Engineers Biotechnol. Prog., 2012
Stereoselective and Diversity‐Oriented Synthesis of Trisubstituted Allylic Alcohols and Amines
Authors: Schmidt Yvonne , Breit Bernhard
Published: September 2011

Stereoselective and diversity‐oriented synthesis of trisubstituted olefins was achieved by using ortho‐diphenylphosphanyl benzoate (o‐DPPB) as a directing group for allylic substitution. The starting point of this methodology was a set of α‐methylene aldehydes derived from Baylis–Hillman adducts. Subsequent addition of different organometallic reagents led to a variety of allylic alcohol substrates. After introduction of the reagent‐directing o‐DPPB group, copper‐mediated allylic substitution with a wide range of Grignard reagents enabled the stereoselective construction of a large number of E‐configured trisubstituted allylic alcohols and amines in excellent yields and stereoselectivities. Remarkable is the synthetic flexibility, which allows a wide range of permutations starting from an aldehyde followed by successive introduction of the substituents R2 and R3 from organometallic Grignard based reagents. Thus, starting from only a few precursors, a diversity‐oriented synthesis of stereodefined trisubstituted allylic alcohols and amines becomes possible.
Combination of targeted agents in metastatic renal cell carcinoma
Authors: Michaelson M. Dror
Published: September 2011

Targeted therapy has favorably changed the standard of care for patients with advanced renal cell carcinoma. However, combinations of targeted therapy have been characterized by excessive toxicity, as exemplified in the report by Molina et al in this issue.
The analysis of the transcriptome as a new approach for biomarker development to trace the abuse of anabolic steroid hormones
Authors: Riedmaier Irmgard , Pfaffl Michael W. , Meyer Heinrich H. D.
Published: September 2011

The abuse of anabolic steroid hormones in human sports and animal husbandry is an ubiquitous problem and therefore a tight control program in both areas is very important. Within these control programs, hormone residues are detected by immunoassays or chromatographical methods in combination with mass spectrometry. With these methods, all known substances can be detected; yet new xenobiotic growth promoters and new ways of application are difficult to detect. Therefore it is important to develop new sensitive screening methods to enable an efficient control for misused anabolic substances. The detection of their physiological action is a promising approach. Anabolic steroid hormones directly influence the expression of specific genes and thus the analysis of the transcriptome of different target tissues and matrices is of great interest. This review describes our recent efforts made concerning the analysis of gene expression changes in different tissues, different species and under different anabolic treatments. Copyright © 2011 John Wiley & Sons, Ltd.
Improved partial least squares models for stability‐indicating analysis of mebeverine and sulpiride mixtures in pharmaceutical preparation: A comparative study
Authors: Darwish Hany W. , Naguib Ibrahim A.
Published: September 2011

Performance of partial least squares regression (PLSR) is enhanced in the presented work by three multivariate models, including weighted regression PLSR (Weighted‐PLSR), genetic algorithm PLSR (GA‐PLSR), and wavelet transform PLSR (WT‐PLSR). The proposed models were applied for the stability‐indicating analysis of mixtures of mebeverine hydrochloride (meb) and sulpiride (sul) in the presence of their reported impurities and degradation products. The work introduced in this paper aims to compare these different chemometric methods, showing the underlying algorithm for each and making a comparison of analysis results. For proper analysis, a 6‐factor, 5‐level experimental design was established resulting in a training set of 25 mixtures containing different ratios of the interfering species. A test set consisting of 5 mixtures was used to validate the prediction ability of the suggested models. Leave one out (LOO) and bootstrap were applied to predict number of PLS components. The GA‐PLSR proposed method was successfully applied for the analysis of raw material (test set 101.03% ± 1.068, 101.47% ± 2.721 for meb and sul, respectively) and pharmaceutical tablets containing meb and sul mixtures (10.10% ± 0.566, 98.16% ± 1.081 for meb and sul). Copyright © 2011 John Wiley & Sons, Ltd.
Competitive binding of Ba2+and Sr2+ to 18‐Crown‐6 in a Receptor with a 1‐Methoxyanthraquinone Analogue as the Other Binding Site
Authors: Banerjee Tanmay , Suresh Moorthy , Ghosh Hirendra N. , Das Amitava
Published: September 2011

Owing to their immense biological significance, development of sensors for the selective detection of alkaline earth metal ions has attracted vast research interest. In this article we have reported the synthesis, characterisation and ion binding studies of a new RuII‐polypyridyl‐crown‐anthraquinone complex (5). Studies confirm selective binding of BaII, SrII and CaII ions, with K > K >> K, over all other metal ions, to the crown ether moiety and not to the methoxy anthraquinone component, the latter being the second binding site available and known for its affinity towards alkaline earth metal ions from one of our previous reports.
Edge‐Bridging and Face‐Bridging Hydrogen Atoms in Trinuclear Rhenium Carbonyl Hydrides
Authors: Li Nan , Xie Yaoming , King R. Bruce , Schaefer Henry F.
Published: September 2011

The structures of the trinuclear rhenium carbonyl hydrides H3Re3(CO)n (n = 12, 11, 10, 9) have been investigated by density functional theory (DFT). The only structure found for H3Re3(CO)12 is the experimentally known structure with each approximately 3.3 Å edge of a singly bonded Re3 triangle bridged by a hydrogen atom and all terminal carbonyl groups. The two lowest energy H3Re3(CO)11 structures lie within 0.5 kcal/mol in energy and are derived from this H3Re3(CO)12 structure by loss of a carbonyl group with retention of the central Re3(μ‐H)3 core. A higher energy H3Re3(CO)11 structure, closely related to the experimental structure for the isoelectronic dianion H3Re3(CO)102–, is also found in which one of the Re=Re edges of double bond length (2.79 Å) is bridged by two hydrogen atoms. Loss of a carbonyl group from this H3Re3(CO)11 structure with concurrent conversion of one of the edge‐bridging hydrogen atoms to a face‐bridging hydrogen atom gives the lowest energy H3Re3(CO)10 structure. Further loss of a carbonyl group from this (μ3‐H)(μ‐H)2Re3(CO)10 structure with concurrent conversion of a second edge‐bridging hydrogen atom to a face‐bridging hydrogen atom leads to the lowest energy H3Re3(CO)9 structure. This (μ3‐H)2(μ‐H)Re3(CO)9 structure with a central Re3(μ3‐H)2 trigonal bipyramid appears to be a very favorable structure since it not only is the lowest energy H3Re3(CO)9 structure but lies more than 22 kcal/mol below the next lowest energy H3Re3(CO)9 structure.
Intermetallic Studies and Bonding Concepts
Authors: Corbett John D.
Published: September 2011

This essay for EurJIC's cluster issue on polar intermetallics, clusters and cluster complexes introduces the reader to the difficulties in finding new and novel intermetallics among a wide variety of possibilities, inasmuch as most of the elements of the periodic table are metals. Like metal atoms may form naked clusters or be differently charged, such as Zintl cations or polyanions. Discrete clusters may also be incorporated as building blocks in polar intermetallics or be condensed into infinite one‐, two‐, or three‐dimensional arrays. In all cases, it is important to explore the unknown before (physical) properties can be measured and applications come into view.
Simplifying biodiesel production: The direct or in situ transesterification of algal biomass
Authors: Haas Michael J. , Wagner Karen
Published: September 2011

The in situ esterification/transesterification of algal biomass lipids to produce FAME for potential use as biodiesel was investigated. Commercial algal biomass was employed, containing 20.9 wt% hexane extractable oil. This consisted of 35.1 wt% free fatty acids (FFA), 18.2 wt% TAG, and 8.8 wt% MAG, accounting for 62.1% of the extractable material. Other constituents of the hexane extractable material, accounting for 37.9% of the extracts, were not further characterized. The predominant fatty acids in the oil were palmitic (42.4 wt%), oleic (30.6 wt%), linoleic (22.8 wt%), and linolenic (16.1 wt%). Small amounts of 10‐keto 16:0 and 10‐OH 16:0 fatty acids were also present. Statistical experimental design was employed to coordinately examine the effects of the amounts of methanol, sulfuric acid, and reaction temperature (23–65°C) on the yield of FAME in 2 h reactions. Three methods of feedstock preparation were examined – as received, oven dried, and water‐washed/dried. For all feedstocks conditions could be identified which were predicted to yield greater than 90% maximum theoretical FAME production. Oven drying the feedstock reduced the amount of methanol required, with 83% of maximum yield obtained at a methanol/fatty acid molar ratio of 220:1 (4 mL methanol/g substrate). Water washing the biomass did not reduce the methanol required for high level transesterification.

Practical applications: In biodiesel production by the conventional method of alkali‐catalyzed transesterification of a refined vegetable oil/the combination of feedstock and process costs threatens the economic viability of biofuel production. In situ esterification/transesterification is a method for producing biodiesel wherein a lipid‐bearing material is directly treated with reagents that catalyze fatty acid alkyl ester production from FFA and acylglycerols. By eliminating the need to isolate and refine the feedstock lipid, this approach to biodiesel production eliminates some of the processing steps required by contemporary methods. This could provide a welcome reduction in the cost of biodiesel production. There is presently considerable interest in the possibility of biofuel production from algal biomass. This study describes the application and optimization of in situ transesterification to a lipid‐bearing algal biomass. Application of this technology could facilitate the economical production of biodiesel from algal biomass.
Regiolone and Isosclerone, Two Enantiomeric Phytotoxic Naphthalenone Pentaketides: Computational Assignment of Absolute Configuration and Its Relationship with Phytotoxic Activity
Authors: Evidente Antonio , Superchi Stefano , Cimmino Alessio , Mazzeo Giuseppe , Mugnai Laura , Rubiales Diego , Andolfi Anna , Villegas‐Fernández Angel M.
Published: September 2011

The absolute configurations of regiolone and isosclerone, two enantiomeric bioactive naphthalenone pentaketides produced by fungi and plants, have been unambiguously assigned by ab initio computational prediction of their theoretical optical rotatory powers and electronic circular dichroism spectra. Isosclerone is produced by the plant pathogen Botrytis cinerea, whereas regiolone is produced by B. fabae. The phytotoxic activities of the two compounds were tested for comparison on faba bean (host of both pathogens) and vine plants (host of only B. cinerea); the (R) configuration at C‐4 was found to be a fundamental structural feature for bioactivity.
Bicomponent Microneedle Array Biosensor for Minimally‐Invasive Glutamate Monitoring
Authors: Windmiller Joshua Ray , Valdés‐Ramírez Gabriela , Zhou Nandi , Zhou Ming , Miller Philip R. , Jin Chunming , Brozik Susan M. , Polsky Ronen , Katz Evgeny , Narayan Roger , Wang Joseph
Published: September 2011

This article describes the design of a new and attractive minimally‐invasive bicomponent microneedle sensing device for the electrochemical monitoring of the excitatory neurotransmitter glutamate and glucose. The new device architecture relies on the close integration of solid and hollow microneedles into a single biosensor array device containing multiple microcavities. Such microcavities facilitate the electropolymeric entrapment of the recognition enzyme within each microrecess. The resulting microneedle biosensor array can be employed as a minimally‐invasive on‐body transdermal patch, obviating the extraction/sampling of the biological fluid, thereby simplifying device requirements. The new concept is demonstrated for the electropolymeric entrapment of glutamate oxidase and glucose oxidase within a poly(o‐phenylenediamine) (PPD) thin film. The PPD‐based enzyme entrapment methodology enables the effective rejection of coexisting electroactive interferents without compromising the sensitivity or response time of the device. The resulting microneedle‐based glutamate and glucose biosensors thus exhibit high selectivity, sensitivity, speed, and stability in both buffer and undiluted human serum. High‐fidelity glutamate measurements down to the 10 µM level are obtained in serum. The attractive recess design also serves to protect the enzyme layer upon insertion into the skin. This simple, yet robust microneedle design is well‐suited for diverse biosensing applications in which real‐time metabolite monitoring is a core requirement.
Characterization of impact odorants and sensory profile of Bobal red wines from Spain's La Mancha region
Authors: Gómez García‐Carpintero E. , Sánchez‐Palomo E. , Gómez Gallego M.A , González‐Viñas M.A.
Published: September 2011

Although the Bobal red grape variety is grown mainly in the Valencia region of Spain, there is also limited production in certain areas of the La Mancha region. Bobal red wines of five consecutive vintages, produced in the La Mancha region, were evaluated by sensory descriptive analysis using a panel of 15 trained assessors. Wines were obtained in standardized conditions and were not aged. Panellists scored the intensity of each attribute using a non‐structured scale. Principal component analysis performed on sensory data showed that these wines were characterized by blackcurrant, green pepper, smoke, redcurrant, cut hay, vanilla and cinnamon aromas. Odour activity values for the various compounds in Bobal wines were classified into seven odorant series describing the aroma profile (1: fruity, 2: floral, 3: green/fresh, 4: sweet, 5: spice, 6: fatty, and 7: other odours). Total intensities for each odorant series were calculated as the sum of the odour activity value for each compound assigned to that series. The fruity and sweet series were found to contribute most to the aroma profile of Bobal wines. Copyright © 2011 John Wiley & Sons, Ltd.
A finite element formulation satisfying the discrete geometric conservation law based on averaged Jacobians
Authors: Storti Mario A. , Garelli Luciano , Paz Rodrigo R.
Published: September 2011

In this article, a new methodology for developing discrete geometric conservation law (DGCL) compliant formulations is presented. It is carried out in the context of the finite element method for general advective–diffusive systems on moving domains using an ALE scheme. There is an extensive literature about the impact of DGCL compliance on the stability and precision of time integration methods. In those articles, it has been proved that satisfying the DGCL is a necessary and sufficient condition for any ALE scheme to maintain on moving grids the nonlinear stability properties of its fixed‐grid counterpart. However, only a few works proposed a methodology for obtaining a compliant scheme. In this work, a DGCL compliant scheme based on an averaged ALE Jacobians formulation is obtained. This new formulation is applied to the θ family of time integration methods. In addition, an extension to the three‐point backward difference formula is given. With the aim to validate the averaged ALE Jacobians formulation, a set of numerical tests are performed. These tests include 2D and 3D diffusion problems with different mesh movements and the 2D compressible Navier–Stokes equations. Copyright © 2011 John Wiley & Sons, Ltd.
A comparative study of two fast nonlinear free‐surface water wave models
Authors: Ducrozet Guillaume , Bingham Harry B. , Engsig‐Karup Allan P. , Bonnefoy Félicien , Ferrant Pierre
Published: September 2011

This paper presents a comparison in terms of accuracy and efficiency between two fully nonlinear potential flow solvers for the solution of gravity wave propagation. One model is based on the high‐order spectral (HOS) method, whereas the second model is the high‐order finite difference model OceanWave3D. Although both models solve the nonlinear potential flow problem, they make use of two different approaches. The HOS model uses a modal expansion in the vertical direction to collapse the numerical solution to the two‐dimensional horizontal plane. On the other hand, the finite difference model simply directly solves the three‐dimensional problem. Both models have been well validated on standard test cases and shown to exhibit attractive convergence properties and an optimal scaling of the computational effort with increasing problem size. These two models are compared for solution of a typical problem: propagation of highly nonlinear periodic waves on a finite constant‐depth domain. The HOS model is found to be more efficient than OceanWave3D with a difference dependent on the level of accuracy needed as well as the wave steepness. Also, the higher the order of the finite difference schemes used in OceanWave3D, the closer the results come to the HOS model. Copyright © 2011 John Wiley & Sons, Ltd.