bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: Pinacol Coupling of Aromatic Aldehydes and Ketones Using Zn—ZnCl2 under Ultrasound.
Authors: Zang Hong‐Jun , Li Ji‐Tai , Ning Ning , Wei Na , Li Tong‐Shuang
Published: June 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
ChemInform Abstract: Catalytic Direct 1,4‐Conjugate Addition of Aldehydes to Vinylketones on Secondary‐Amines Immobilized in FSM‐16 Silica.
Authors: Shimizu Ken‐ichi , Suzuki Hiromasa , Hayashi Eidai , Kodama Tatsuya , Tsuchiya Yoshimi , Hagiwara Hisahiro , Kitayama Yoshie
Published: June 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
ChemInform Abstract: Synthesis and Structure of New Triphenylphosphine π‐Complexes of Palladium(0) with p‐Benzoquinone and Their Role in the Oxidative Carbonylation of Alkynes.
Authors: Kulik Alexander V. , Bruk Lev G. , Temkin Oleg N. , Khabibulin Vildar R. , Belsky Vitaly K. , Zavodnik Valery E.
Published: June 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
ChemInform Abstract: Rapid and Efficient Acetylation of Alcohols and Phenols with Acetic Anhydride Using Tin(IV) Porphyrin as Catalyst.
Authors: Tangestaninejad Shahram , Habibi Mohammad Hossein , Mirkhani Valiollah , Moghadam Majid
Published: June 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Werkzeug für die Chemische Biologie. Semisynthese
Authors: Arndt Hans‐Dieter , Hackenberger Christian , Schwarzer Dirk
Published: June 2010

Semisynthetische Verfahren haben einen großen Beitrag zu der rasanten Entwicklung geleistet, die auf dem noch jungen Feld der Chemischen Biologie in den letzten Jahren stattgefunden haben. Dabei haben beeindruckende Beispiele für die Semisynthese von komplexen modifizierten Proteinen sowie die Derivatisierung von Naturstoffen für biologische Studien nicht nur die Grenzen des Machbaren immer weiter verschoben, sondern auch tatsächlich effiziente Werkzeuge zur Erforschung von Proteinfunktionen etabliert. Gerade für Anwendungen in der Proteomik, das Studium zellulärer Zusammenhänge und ihrer Quantifizierung sind von semisynthetischen Ansätzen weitere Impulse zu erwarten. Dabei zeichnet sie besonders ein interdisziplinärer Charakter aus, der Chemie und Biologie verknüpft. Es ist zu erwarten, dass die wissenschaftliche Bedeutung dieser Verfahren weiter zunehmen wird.
Elevated pretreatment serum concentration of YKL‐40—An independent prognostic biomarker for poor survival in patients with metastatic nonsmall cell lung cancer
Authors: Thöm Ina , Andritzky Birte , Schuch Gunter , Burkholder Iris , Edler Lutz , Johansen Julia S. , Bokemeyer Carsten , Schumacher Udo , Laack Eckart
Published: June 2010

BACKGROUND:

The glycoprotein YKL‐40 is synthesized both by cancer cells and by tumor‐associated macrophages and plays a functional role in tumor progression. Consequently, high serum YKL‐40 levels have been associated with a poor prognosis in patients with several cancer types. However, the role of YKL‐40 has not been established in nonsmall cell lung cancer (NSCLC).

METHODS:

Pretreatment serum levels of YKL‐40 were determined in 189 patients with NSCLC (143 men and 46 women; median age, 62 years;, age range, 41‐76 years). Twelve percent of patients had stage IIIB disease, and 88% had stage IV disease. Ninety‐eight patients received combined gemcitabine and vinorelbine, and 91 received combined gemcitabine, vinorelbine, and cisplatin as first‐line chemotherapy. The median overall survival was 37 weeks.

RESULTS:

Patients had a median serum YKL‐40 level of 209 ng/mL (range, 19‐2153 ng/mL). No correlation was observed between overall survival and the type of chemotherapy regimen used, tumor stage, sex, or histologic types. Patients with high serum YKL‐40 levels (greater than the median level for all patients [209 ng/mL]) had a significantly shorter survival than patients with serum YKL‐40 levels below the median (median survival, 32 weeks vs 41 weeks; P = .007). In multivariate analysis, the serum YKL‐40 level, the presence of bone lesions, and the serum lactate dehydrogenase level were independent, statistically significant prognostic factors.

CONCLUSIONS:

The pretreatment serum YKL‐40 level was identified as a new, independent prognostic biomarker in patients with metastatic NSCLC and may help to determine the individual prognosis of these patients. Cancer 2010. © 2010 American Cancer Society.
Phase 1 and pharmacokinetic study of everolimus, a mammalian target of rapamycin inhibitor, in combination with docetaxel for recurrent/refractory nonsmall cell lung cancer
Authors: Ramalingam Suresh S. , Harvey R. Donald , Saba Nabil , Owonikoko Taofeek K. , Kauh John , Shin Dong M. , Sun Shi‐Yong , Strychor Sandra , Tighiouart Mourad , Egorin Merrill J. , Fu Haian , Khuri Fadlo R.
Published: June 2010

BACKGROUND:

Everolimus is a novel inhibitor of the mammalian target of rapamycin pathway, which is aberrantly activated in nonsmall cell lung cancer (NSCLC). The authors conducted a phase 1 and pharmacokinetic study of everolimus and docetaxel for recurrent NSCLC.

METHODS:

Patients with advanced stage NSCLC and progression after prior platinum‐based chemotherapy were eligible. Sequential cohorts were treated with escalating doses of docetaxel (Day 1) and everolimus (orally daily, Days 1‐19) every 3 weeks. Pharmacokinetic sampling of everolimus and docetaxel was done in Cycle 1. The primary endpoint was determination of the recommended phase 2 doses of the combination.

RESULTS:

Twenty‐four patients were enrolled (median age, 62 years; women, 11; number of prior regimens, 1 [n = 13], 2 [n = 6], ≥3 [n = 5]; Eastern Cooperative Oncology Group performance status, 0 [n = 6], 1 [n = 17]). The dose‐limiting toxicities (DLTs) were fever with grade 3/4 neutropenia, grade 3 fatigue, and grade 3 mucositis. None of the 7 patients treated at the recommended phase 2 dose (docetaxel 60 mg/m2 and everolimus 5 mg daily) experienced DLT. Everolimus area under the concentration time curve (AUC) was not different with 60 or 75 mg/m2 docetaxel. Mean ± standard deviation AUC‐based accumulation factors for everolimus on Days 8 and 15 were 1.16 ± 0.37 and 1.42 ± 0.42, respectively. Docetaxel Day 1 half‐life was 9.4 ± 3.4 hours. Among 21 patients evaluable, 1 had a partial response, and 10 had disease stabilization.

CONCLUSIONS:

The recommended phase 2 doses of docetaxel and everolimus for combination therapy are 60 mg/m2 and 5 mg orally daily, respectively. Promising anticancer activity has been noted. Cancer 2010. © 2010 American Cancer Society.
Diffuse reflectance‐factor measurements of rose petals
Authors: Rao Gottipaty , Garofalo James , Lanides Elias
Published: June 2010

The diffuse reflectance factor for different colored rose petals is measured as a function of wavelength using a high resolution optical spectrometer. The tristimulus values, the CIE chromaticity coordinates, the dominant wavelength and purity, the CIE whiteness index, the tint index, the CIE 1976 LAB coordinates, as well as CIELAB hue‐angle and chroma are reported. The data on diffuse reflectance factor are presented in the 390−800 nm range at intervals of 10 nm. Using the data, one can generate the perceived color of the roses and the color coordinates in different illuminating light sources and environments. The present data will be useful for the color characterization of flowers, realistic rendering of flowers in computer graphics, color photography, and in the development of filters for color photography. © 2010 Wiley Periodicals, Inc. Col Res Appl, 2011
Conceptual Approach to the Reactivity of Dihydrogen
Authors: Berke Heinz
Published: June 2010

Dihydrogen reactions are mainly reaction‐center‐mediated. In a systematic approach, these reactions are divided into the steps of splitting of H2 and H‐atom transfers with homolytic and heterolytic splitting at mono‐ and dinuclear reaction centers, and further homopolar H transfers in Wilkinson‐type hydrogenations (insertion and reductive elimination) and heteropolar transfers in ionic hydrogenations (hydride before proton, proton before hydride, simultaneous hydride/proton transfers). Based on these categories, transfer hydrogenations are also surveyed. A separate class of reactions is one‐electron reactions of dihydrogen.
Theoretical Study of the Reactions M++CH3F (M=Ge, As, Se, Sb)
Authors: Méndez Oscar , Colmenares Fernando
Published: June 2010

CASSCF–MRMP2 calculations have been carried out to analyze the reactions of the methyl fluoride molecule with the atomic ions Ge+, As+, Se+ and Sb+. For these interactions, potential energy curves for the low‐lying electronic states were calculated for different approaching modes of the fragments. Particularly, those channels leading to CH and CF oxidative addition products, H2FCMH+ and H3CMF+, respectively were explored, as well as the paths which evolve to the abstraction (MF++CH3) and the elimination (CH2M++HF) asymptotes. For the reaction Ge++CH3F the only favorable channel leads to fluorine abstraction by the ion. As+ and Sb+ can react with CH3F along pathways yielding stable addition products. However, a viable path joining the oxidative addition product H3CMF+ with the elimination asymptote CH2M++HF was found for the reaction of the fluorocarbon compound with As+. No favorable channels were detected for the interaction of fluoromethane with Se+. The results discussed herein allow rationalizing some of the experimental data found for these interactions through gas‐phase mass spectrometry.
Early exposure to odors changes later visual prey preferences in cuttlefish
Authors: Guibé Mathieu , Boal Jean G. , Dickel Ludovic
Published: June 2010

Developmental studies have shown that environmental stimulation received by a developing sensory system can alter the developmental outcome of both that sensory system and other aspects of the nervous system. We investigated the ecologically relevant question of whether prior exposure to prey early in development within one sensory modality could influence later prey choice within a different sensory modality. Cuttlefish are visual predators; they can detect prey odors but attacks on prey cannot be elicited without visual stimulation. Cuttlefish eggs were exposed to the odor of shrimp (preferred prey), crabs (non‐preferred prey), mollusks (non‐prey), or a seawater control (no prey). Seven days after hatching, prey preferences were tested with a visual choice test between crabs and shrimp. Hatchlings exposed to crabs odors and the seawater control were significantly more likely to attack shrimp. Hatchlings exposed to mollusk odors showed no visual prey preference, while those exposed to shrimp preferentially attacked crabs. These results demonstrate a complex relationship between an early sensory exposure and later prey preference. © 2010 Wiley Periodicals, Inc. Dev Psychobiol 52: 833–837, 2010.
Bericht über die 70. Sitzung des Ständigen Ausschusses für das Bauwesen
Authors: Springborn Matthias
Published: June 2010

Am 26. und 27. Januar 2010 fand die 70. Sitzung des Ständigen Ausschusses für das Bauwesen (StAB) in Brüssel statt. Den Vorsitz hatte der Leiter des Referats “Baugewerbe” bei den Kommissionsdiensten.

Im Folgenden werden die wesentlichen Beratungsinhalte kurz wiedergegeben.
Elevated corticosterone levels in stomach milk, serum, and brain of male and female offspring after maternal corticosterone treatment in the rat
Authors: Brummelte Susanne , Schmidt Kim L. , Taves Matthew D. , Soma Kiran K. , Galea Liisa A.M.
Published: June 2010

Early influences such as maternal stress affect the developmental outcome of the offspring. We created an animal model of postpartum depression/stress based on giving high levels of corticosterone (CORT) to the rat dam, which resulted in behavioral and neural changes in the offspring. This study investigated whether highly elevated levels of maternal CORT during pregnancy or the postpartum result in higher levels of CORT in the stomach milk, serum, and brain of offspring. Dams received daily injections of CORT (40 mg/kg) or oil (control) either during pregnancy (gestational days 10–20) or the postpartum (Days 2–21). Pups that were exposed to high gestational maternal CORT had higher CORT levels in serum, but not in stomach milk or brain, on postnatal day (PND) 1. However, on PND7, pups that were exposed to high postpartum maternal CORT had higher CORT levels in stomach milk and brain, but not in serum. Conversely on PND18, pups that were exposed to high postpartum maternal CORT had higher CORT levels in serum, but not in brain (prefrontal cortex, hypothalamus, or hippocampus). Moreover, 24 h after weaning, there were no significant differences in serum CORT levels between the groups. Thus, CORT given to the dam during pregnancy or the postpartum results in elevated levels of CORT in the offspring, but in an age‐ and tissue‐dependent manner. Developmental exposure to high CORT could reprogram the HPA axis and contribute to the behavioral and neural changes seen in adult offspring. © 2010 Wiley Periodicals, Inc. Develop Neurobiol 70: 714–725, 2010
Molecular Haeckel
Authors: Elinson Richard P. , Kezmoh Lorren
Published: June 2010

More than a century ago, Ernst Haeckel created embryo drawings to illustrate the morphological similarity of vertebrate early embryos. These drawings have been both widely presented and frequently criticized. At the same time that the idea of morphological similarity was recently attacked, there has been a growing realization of molecular similarities in the development of tissues and organs. We have surveyed genes expressed in vertebrate embryos, and we have used them to construct drawings that we call Molecular Haeckels. The Molecular Haeckels emphasize that, based on gene expression, there is a greater similarity among vertebrate embryos than even Haeckel might have imagined. Developmental Dynamics 239:1905–1918, 2010. © 2010 Wiley‐Liss, Inc.
The outcome of cross‐priming during virus infection is not directly linked to the ability of the antigen to be cross‐presented
Authors: Alatery Attiya , Tarrab Esther , Lamarre Alain , Basta Sameh
Published: June 2010

The initiation of CD8+ T cell (CTL) immune responses can occur via cross‐priming. Recent data suggested a relationship between cross‐presentation and immunodominance of epitope‐specific T cells. To test this association, we evaluated the efficacy of cross‐presentation for several virus epitopes in vitro and examined if this can be extrapolated in vivo. Employing lymphocytic choriomeningitis virus (LCMV), we demonstrate that the cross‐presentation and cross‐priming of LCMV antigens were dominated by NP396, but not NP205 when analyzing the LCMV‐NP. Although with LCMV‐GP, cross‐presentation was dominated by GP276, and cross‐priming was dominated by GP33. Importantly, although NP396 was significantly more efficient than GP33 in cross‐presentation, cross‐priming of their specific CTL was comparable. In a subsequent virus challenge after cross‐priming, GP33‐specific CTL dominated the response. Accordingly, based on our data, the ability of viral epitopes to be cross‐presented in vitro does not entirely reflect what would occur in cross‐priming. Thus, weak cross‐presenting antigens may still cross‐prime an efficient CTL response depending on other in vivo elements such as the naïve T‐cell precursor frequencies.
Enhanced protection to Mycobacterium tuberculosis infection in IL‐10‐deficient mice is accompanied by early and enhanced Th1 responses in the lung
Authors: Redford Paul S. , Boonstra Andre , Read Simon , Pitt Jonathan , Graham Christine , Stavropoulos Evangelos , Bancroft Gregory J. , O'Garra Anne
Published: June 2010

IL‐10 regulates the balance of an immune response between pathogen clearance and immunopathology. We show here that Mycobacterium tuberculosis (Mtb) infection in the absence of IL‐10 (IL‐10−/− mice) results in reduced bacterial loads in the lung. This reduction was preceded by an accelerated and enhanced IFN‐γ response in the lung, an increased influx of CD4+ T cells into the lung, and enhanced production of chemokines and cytokines, including CXCL10 and IL‐17, in both the lung and the serum. Neutralization of IL‐17 affected neither the enhanced production of CXCL10 nor the accumulation of IFN‐γ‐producing T cells in the lungs, but led to reduced numbers of granulocytes in the lung and reduced bacterial loads in the spleens of Mtb‐infected mice. This suggests that IL‐17 may contribute to dissemination of Mtb.
The Adaptable Coordination Chemistry of 6‐Chloro‐2‐(quinolin‐2‐yl)‐2,4‐dihydro‐1H‐benzo[d][1,3]oxazine Towards Zinc(II) and Mercury(II)
Authors: Ardizzoia G. Attilio , Brenna Stefano , Therrien Bruno
Published: June 2010

The coordination chemistry of 6‐chloro‐2‐(quinolin‐2‐yl)‐2,4‐dihydro‐1H‐benzo[d][1,3]oxazine (LH2) towards zinc and mercury has been explored. The ligand exhibits high versatility and provides different environments to the metal centre as a function of its diverse coordination modes. In one of the isolated and characterized complexes, [Zn(LOH)Cl2], the zinc centre is found pentacoordinated with the ligand present in an iminic “open” structure. The oxidized form, which contains the 4H‐benzo[d][1,3]oxazine part (L), is also encountered in [Zn(L)Cl2], whereas the crystal structure of the trinuclear compound [Hg3(LH2)2Cl6] shows the ligand LH2 in its original arrangement.
Preparation of Cobalt‐Containing Ligands with NHC‐ and/or P‐Coordinating Sites and Their Application in Heck Reactions: The Formation of an Unexpected Cobalt‐Containing Zwitterionic Complex
Authors: Guo Chi‐Shing , Weng Chia‐Ming , Hong Fung‐E
Published: June 2010

An unexpected cobalt‐containing zwitterionic complex, [{(μ‐PPh2CH2PPh2)Co2(CO)4}{μ,η‐(R1)PC≡CCH2(R2)}] (8; R1 = Ph2Bz; R2 = 3‐CoBr3‐1‐benzimidazole), has been obtained during an attempt to modify the imidazole moiety in the alkyne‐bridging dicobalt complex [{(μ‐PPh2CH2PPh2)Co2(CO)4}{μ,η‐Ph2PC≡CCH2(IM)}] (5; IM = benzimidazole) to a carbene‐type substituent by reaction with benzyl bromide. As revealed in the crystal structure of 8, it is clear that the benzyl bromide was nucleophilically attacked by the phosphane moiety of 5 with the result the addition of the benzyl moiety. This phosphane site in 8 is in a tetrahedral environment and presumably cationic in nature. In addition, an unusual anionic species CoBr3– was found to have attached itself to the free nitrogen site of the imidazole moiety. Thus 8 can be regarded as an unusual metal‐containing zwitterionic complex. When the phosphane site of 5 was replaced by a non‐reactive substituent, for example, [{(μ‐PPh2CH2PPh2)Co2(CO)4}{μ,η‐RC≡CCH2(IM)}] (5′: R = H; 5­­_O: R = Ph2(O)P), nucleophilic attack took place exclusively on the imidazole moiety and led to the formation of [{(μ‐PPh2CH2PPh2)Co2(CO)4}{μ,η‐RC≡CCH2(IM′)}+]Br– [9′: R = H; 9_O: R = Ph2(O)P; IM′ = 3‐benzyl‐1H‐benzimidazole]. Complex 9′ could act as a carbene precursor, which was demonstrated by the formation of the bis‐9′‐coordinated palladium complex [trans‐({(μ‐PPh2CH2PPh2)Co2(CO)4}{μ,η‐HC≡CCH2(IM′)})2PdBr2] (11) on treatment with [Pd(cod)Cl2]. Fair‐to‐good efficiencies were observed in Heck reactions employing either isolated 11 or in situ 9′/PdCl2 (2:1) as the catalytic precursor.
Better Performance of Monodentate P‐Stereogenic Phosphanes Compared to Bidentate Analogues in Pd‐Catalyzed Asymmetric Allylic Alkylations
Authors: Grabulosa Arnald , Muller Guillermo , Ceder Rosa , Maestro Miguel Ángel
Published: June 2010

The cationic allylpalladium complexes 3a–3f, 4a, 4e, 5e of type [Pd(η3‐2‐Me‐C3H4)P2]PF6 were synthesized using a group of monodentate P‐stereogenic phosphanes, P=PPhRR′ (a–f) and diphosphanes (PhRPCH2)2 (1a, 1e) or PhRPCH2Si(Me)2CH2PPhR (2e). The analogous cationic complexes with the disubstituted allyl group (η3‐1,3‐Ph2‐C3H3) and monodentate phosphanes were not isolated as stable solids; only [PdCl(η3‐1,3‐Ph2‐C3H3)P] (6a, 6d) were obtained. Palladium allyl complexes were screened as precatalysts in the allylic substitution of rac‐3‐acetoxy‐1,3‐diphenyl‐1‐propene (I) and (E)‐3‐acetoxy‐1‐phenyl‐1‐propene (III) with dimethyl malonate as the nucleophile. The various catalytic precursors showed a wide range of activity and selectivity. The bismonodentate phosphane complexes 3 are more active than the bidentate analogues. With regard to the regioselectivity, precursors containing monodentate phosphanes favour the formation of the linear product in the allylic substitution of cinnamyl acetate (III) compared with those containing bidentate phosphanes. With substrate I, compounds with the diphosphanes 1a and 1e, containing a five‐membered chelate ring, gave low enantioselectivities (less than 10 % ee), but those with the diphosphane 2e, forming a six‐membered chelate ring or with two monodentate phosphanes, afforded products with moderate enantioselectivity under standard conditions (ee up to 74 %). The results show that the performance of precursors containing monodentate phosphanes was superior to those containing bidentate ligands in both activity and selectivity.
Lanthanide Complexes Coordinated by a Dianionic Bis(amidinate) Ligand with a Rigid Naphthalene Linker
Authors: Yakovenko Marina V. , Cherkasov Anton V. , Fukin Georgy K. , Cui Dongmei , Trifonov Alexander A.
Published: June 2010

The synthetic pathway to a new bis(amidine) ligand with a conformationally rigid naphthalene linker, 1,8‐C10H6[NHC(tBu)=N(2,6‐Me2–C6H3)][N=C(tBu)NH(2,6‐Me2–C6H3)] (3) was elaborated. Deprotonation of this bis(amidine) ligand with two equivalents of nBuLi and subsequent reaction with anhydrous LnCl3 (Ln = Y, Nd, Sm) allowed the synthesisof the chlorido complexes [1,8‐C10H6{NC(tBu)N‐2,6‐Me2–C6H3}2]YCl(dme) (4), [1,8‐C10H6{NC(tBu)N‐2,6‐Me2–C6H3}2]Nd(dme)(μ‐Cl)2Li(dme) (5), and [1,8‐C10H6{NC(tBu)N‐2,6‐Me2–C6H3}2]Sm(thf)(μ‐Cl)2Li(thf)2 (6), which are coordinated by the linked dianionic bis(amidinate) ligand. The structures of complexes 4–6 were established by X‐ray diffraction studies, which reveal that the new ligand framework can coordinate to the lanthanide atoms in different fashions depending on the central atom ion size. Alkylation of complex 6 with equimolar amounts of LiCH2SiMe3 afforded the unexpected amido–amidinate complex [{1,8‐C10H6(NC(tBu)N‐2,6‐Me2–C6H3)2}{1,8‐C10H6(NC(tBu)N‐2,6‐Me2–C6H3)(NH)}Sm][Li(dme)3] (7), which obviously results from the cleavage of one amidinate group during decomposition of the transient alkyl species and ligand redistribution.
Germanate Frameworks Constructed from Oxo Germanium Cluster Building Units
Authors: Lin Zhi‐En , Yang Guo‐Yu
Published: June 2010

This article describes the recent research progress in the field of crystalline germanate frameworks with oxo germanium clusters as building units. By using different amine molecules or transition‐metal complexes as the structure‐directing agents, new oxo germanium clusters, such as Ge7, Ge8, Ge9, Ge10, and Ni@Ge14 units, have been prepared and organized into extended frameworks with chain‐like, tubular, layered, slab‐like, and three‐dimensional structures. The combination of different types of oxo germanium clusters in the same crystalline framework provides an additional way to tune the framework structures. Besides their rich structural chemistry, the germanate frameworks exhibit interesting properties including ion‐exchange, microporosity, and thermal stability, suggesting their potential application in molecular sieving and catalysis.
Characterization of “Cd10S4(SPh)12”, the Thermal Decomposition Product of (NMe4)4[Cd10S4(SPh)16]: Synthesis of a Neutral Cd54 Sulfide Cluster and of a Polymeric Chain of Thiolate‐Bridged Cd17 Sulfide Clusters
Authors: Bendova Maria , Puchberger Michael , Schubert Ulrich
Published: June 2010

Contrary to claims in the literature that a cluster of the composition of “Cd10S4(SPh)12” was formed by thermal treatment of (NMe4)4[Cd10S4(SPh)16], experimental evidence was gathered that the core structure of the cluster is not exclusively retained and other CdS species are also formed. When “Cd10S4(SPh)12” was treated with PhSH/NEt3 only a part of the material was converted into (NHEt3)4[Cd10S4(SPh)16]. From solutions of “Cd10S4(SPh)12” in strongly coordinating solvents the new neutral CdS clusters Cd54S28(SPh)52Lx (L = pyridine, DMSO or DMF) and [Cd17S4(SPh)26py]∞ were crystallized. The latter forms polymeric chains of phenylthiolate‐bridged Cd17 units.
Dichotomous Reactivity in the Reaction of Triethyl‐ and Triphenylphosphane HBr Salts with Dimethyl Acetals: A Novel Entry to α‐Alkoxy‐Functionalized Ylides and General Synthesis of Vinyl Ethers and Alkoxy Dienes
Authors: Das Priyabrata , McNulty James
Published: June 2010

The discovery of dichotomous reactivity in the reaction of trialkyl‐ vs. triphenylphosphane HBr salts with acetals allows entry to functionalized α‐methoxy phosphonium salts and a novel process for tertiary phosphane methylation. The new protocol opens a general entry to the synthesis of vinyl ethers and differentially substituted 1,3‐dienes via Wittig reactions of the functionalized ylides derived from the α‐methoxy phosphonium salts.
Morphology and Electrochemical Properties of the Bismuth Film Electrode Ex Situ Electrochemically Plated from Perchloric Acid
Authors: Bobrowski Andrzej , Królicka Agnieszka , Zarębski Jerzy
Published: June 2010

The performance of a bismuth film electrodes (BiFEs) plated ex situ from 0.17 M Bi(III) in 1.0 M HClO4 in anodic (ASV) and catalytic adsorptive stripping voltammetry (CAdSV) has been demonstrated. The BiFEs were prepared by plating bismuth on the glassy carbon support at the deposition potentials of −0.3 V and −1.0 V, for two charges: 10 mC or 25 mC. The morphology of the films was examined via scanning electron microscopy (SEM), and their electrochemical characteristics were investigated by differential pulse (DPV) and square wave (SWV) stripping voltammetry. The ASV responses of Cd(II), Pb(II), In(III), Tl(I) and the catalytic AdSV response of Ti(IV) ions were examined. The morphology of the deposits was evaluated and its influence on the Cd(II) and Ti(IV) voltammetric responses was discussed.
A Host‐Guest‐Recognition‐Based Electrochemical Sensor for Sequence‐Specific DNA Detection
Authors: Fan Hao , Xing Rong , Wang Xiuhua , Xu Ying , Wang Qingjiang , He Pingang , Fang Yuzhi
Published: June 2010

We herein constructed a sensor that converts target DNA hybridization‐induced conformational transformation of the probe DNA to electrochemical response based on host‐guest recognition and nanoparticle label. In the sensor, the hairpin DNA terminal‐labeled with 4‐((4‐(dimethylamino)phenyl)azo)benzoic acid (dabcyl) and thiol group was immobilized on Au electrode surface as the probe DNA by Au‐S bond, and the CdS nanoparticles surface‐modified with β‐cyclodextrins (CdS‐CDs) were employed as electrochemical signal provider and host‐guest recognition element. Initially, the probe DNA immobilized on electrode kept the stem‐loop configuration, which shielded dabcyl from docking with the CdS‐CDs in solution due to the steric effect. After target hybridization, the probe DNA underwent a significant conformational change, which forced dabcyl away from the electrode. As a result, formerly‐shielded dabcyl became accessible to host‐guest recognition between β‐cyclodextrin (β‐CD) and dabcyl, thus the target hybridization event could be sensitively transduced to electrochemical signal provided by CdS‐CDs. This host‐guest recognition‐based electrochemical sensor has been able to detect as low as picomolar DNA target with excellent differentiation ability for even single mismatch.
Homocysteine Voltammetry at a Mercury Electrode in the Presence of Nickel Ions
Authors: Galík Michal , Bănică Florinel‐Gabriel , Bănică Ana , Švancara Ivan , Vytřas Karel
Published: June 2010

At a mercury electrode, Hcy and Cys yield similar cathodic stripping peaks connected to the reduction of the pertinent mercury thiolate. However, due the different behavior as a ligand for nickel ion, the above compounds perform very differently in the presence of this ion. Whereas the nickel ion at a high enough concentration suppresses the Cys peak, in the case of Hcy it causes the cathodic peak to shift to more negative potentials. The peculiar behavior of Hcy is due to the stabilization of the mercury thiolate surface layer by intermolecular Ni2+ bridges within the surface layer. Conversely, in the case of Cys, the nickel ion strongly competes with the mercury ion and leads to the formation of a surface adsorbed bis‐cysteinatonickelate complex, which prevents the formation of mercury cysteinate. Such a difference allows determining Hcy by cathodic stripping voltammetry in the presence of nickel ion with no Cys interference.
Nonenzymatic Electrochemical Glucose Sensor Based on Pt Nanoparticles/Mesoporous Carbon Matrix
Authors: Su Chang , Zhang Cheng , Lu Guoqiang , Ma Chunan
Published: June 2010

A nonenzymatic amperometric sensor for sensitive and selective detection of glucose has been constructed by using highly dispersed Pt nanoparticles supported onto mesoporous carbons (MCs). The Pt nanoparticles/mesoporous carbons (Pt/MCs) composites modified electrode displayed high electrocatalytic activity towards the oxidation of glucose. At an applied potential of 0.1 V, the Pt/MCs electrode has a linear dependence (R=0.996) in the glucose concentration up to 7.5 mM with a sensitivity of 8.52 mA M−1 cm−2. The Pt/MCs electrode has also shown highly resistant toward poisoning by chloride ions and without interference from the oxidation of common interfering species.
Comparative Study of the Determination of Parabens in Shampoos by Liquid Chromatography with Amperometric and Coulometric Detection
Authors: Murakami Kazuo , Watanabe Hayaki , Tateno Tsuyako , Kauffmann Jean‐Michel
Published: June 2010

The simultaneous determination of four para‐hydroxybenzoic acid esters (parabens) in shampoos was studied by liquid chromatography (LC) with amperometric (LC‐AD) and coulometric (LC‐CD) detection. The parabens were separated on an ODS C18 reversed column by isocratic elution with a mobile phase based on methanol‐0.1 M acetic acid (60 : 40%, v/v) with 0.02 M NaClO4 at a flow rate of 0.8 mL min−1. The limit of detection (S/N>3) for the analytes was in the 15–25 pg (injected mass) range at an applied potential of 1.20 V vs. Ag/AgCl using the LC‐AD and in the 2–3 pg range at a potential of 0.790 V vs. Pd using the LC‐CD. The peak ratio of the internal standard peak (IS: 4‐hydroxybenzoic acid sec‐butyl ester) versus the analyte peak was found to be related to the amount injected from 0.1 ng to 100ng (r=0.996–0.999) with the LC‐AD and from 0.050 ng to 100 ng range (r=0.999–1.000) with the LC‐CD. The relative standard deviation (RSD, n=10) was comprised between 1.8 to 3.5% by LC‐AD ( 5 ng injected) and between 2.0 to 2.4% by LC‐CD (0.5 ng injected). The determination of four most used parabens in ten different shampoos was successfully realized.
Sedimentary evidence of Late Holocene human activity in the Pearl River delta, China
Authors: Zong Y. , Yu F. , Huang G. , Lloyd J. M. , Yim W. W.‐S.
Published: June 2010

This study examines the sedimentary evidence of human activities during the last 4000 years in the Pearl River deltaic area. The analyses are focused on indentifying agricultural signatures present in the sedimentary record and establishing the timing of a change from a simple, rice‐based agriculture to a more advanced, diverse agriculture. The examination is based on modern sediment and plant samples and a sediment core collected from the deltaic area. The analyses include particle size and diatom analysis to determine the environmental conditions that were associated with the period of human activities. Organic carbon isotope ratios and major metal elements reveal an expansion in commercial crop production and metal smelting in the Pearl River delta area about 2000 years ago. The input of organic matter from introduced sugarcane, a C4 plant, elevates the bulk organic carbon isotope values in the estuarine sediments above that represented by other common agricultural crops in the study area, including rice, banana and lotus, which are all C3 plants. The increase in bulk organic isotopic value coincides with the rise in the concentration of copper, iron and lead in the sedimentary sequence, suggesting a wider use of metal tools. These results indicate that advanced agriculture started about 2000 years ago as an expansion in human population took place in the area. This record also provides sedimentary evidence that help ascertain the timing and type of human activities that are linked to subsequent land reclamation on the deltaic plain, resulting in rapid shoreline advancement in the last 2000 years. Copyright © 2010 John Wiley & Sons, Ltd.
Ovarian cycle and embryonic development inGammarus fossarum: Application for reproductive toxicity assessment
Authors: Geffard Olivier , Xuereb Benoit , Chaumot Arnaud , Geffard Alain , Biagianti Sylvie , Noël Claire , Abbaci Khedidja , Garric Jeanne , Charmantier Guy , Charmantier-Daures Mireille
Published: June 2010

Among freshwater invertebrates, Gammarus fossarum is an important test organism and is currently used in ecotoxicology for acute and chronic assays; nevertheless, reproductive toxicity test methods are not yet available for these species. In the present study, the reproductive cycle in Gammarus fossarum was characterized in order to propose a reproductive toxicity test encompassing molting, follicle growth, and embryonic development that will provide a better understanding of the mode of action of chemicals disrupting these hormone-regulated processes. A detailed description of the reproductive cycle in Gammarus fossarum was obtained. As in some amphipods, molt and reproductive cycles of G. fossarum females occur concurrently, lasting 30 d at 12°C. Each molt stage is characterized by a specific marsupial embryonic development stage and the size of developing follicles visible on the ovarian membrane. Based on these results, a 21-d reproductive toxicity test is proposed for this species. This new bioassay was applied to identify the specific impact of different stressors: cadmium, methomyl, nonylphenol, and a starvation diet. Good reproducibility was obtained for different endpoints under control conditions and throughout the experiments. Preliminary robust reference values or benchmarks were proposed for these endpoints. Cadmium was found to specially inhibit secondary vitellogenesis. Nonylphenol had a specific concentration-dependent effect on embryonic development, with an increase in the percent abnormality from a concentration of 0.05 µg/L. A restricted food diet led to a significant delay in the molt cycle, which in turn induced inhibition of secondary vitellogenesis. Environ. Toxicol. Chem. 2010;29:2249–2259. © 2010 SETAC
Characterization of acetylcholinesterase from the brain of the Amazonian tambaqui (Colossoma macropomum) and in vitro effect of organophosphorus and carbamate pesticides
Authors: Assis Caio Rodrigo Dias , Castro Patrícia Fernandes , Amaral Ian Porto Gurgel , Carvalho Elba Verônica Matoso Maciel , Carvalho Luiz Bezerra , Bezerra Ranilson Souza
Published: June 2010

In the present study, acetylcholinesterase (AChE) from the brain of the Amazonian fish tambaqui (Colossoma macropomum) was partially characterized and its activity was assayed in the presence of five organophosphates (dichlorvos, diazinon, chlorpyrifos, and tetraethyl pyrophosphate [TEPP]) and two carbamates (carbaryl and carbofuran) insecticides. Optimal pH and temperature were 7.0 to 8.0 and 45°C, respectively. The enzyme retained approximately 70% of activity after incubation at 50°C for 30 min. The insecticide concentration capable of inhibiting half of the enzyme activity (IC50) for dichlorvos, chlorpyrifos, and TEPP were calculated as 0.04 µmol/L, 7.6 µmol/L, and 3.7 µmol/L, respectively. Diazinon and temephos did not inhibit the enzyme. The IC50 values for carbaryl and carbofuran were estimated as 33.8 µmol/L and 0.92 µmol/L, respectively. These results suggest that AChE from the juvenile C. macropomum brain could be used as an alternative biocomponent of organophosphorus and carbamate biosensors in routine pesticide screening in the environment. Environ. Toxicol. Chem. 2010;29:2243–2248. © 2010 SETAC
Flame Spray Synthesis of Nanoscale La0.6Sr0.4Co0.2Fe0.8O3–δ and Ba0.5Sr0.5Co0.8Fe0.2O3–δ as Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells
Authors: Heel A. , Holtappels P. , Hug P. , Graule T.
Published: June 2010

Electrochemical performance and degradation was analysed by conductivity measurements as well as thermogravimetric analysis (TGA) under different atmospheres. CO2 was identified as a critical parameter in terms of carbonate formation from Ba0.5Sr0.5Co0.8Fe0.2O3–δ and causes a strong increase in the material resistivity, whereas La0.6Sr0.4Co0.2Fe0.8O3–δ is unaffected. The oxygen exchange kinetic of both compositions is affected by CO2 containing atmospheres.
NOV/CCN3 upregulates CCL2 and CXCL1 expression in astrocytes through β1 and β5 integrins
Authors: Le Dréau G. , Kular L. , Nicot A.B. , Calmel C. , Melik‐Parsadaniantz S. , Kitabgi P. , Laurent M. , Martinerie C.
Published: June 2010

Increasing evidence suggests that CCN matricellular proteins play important roles in inflammation. One of the major cell types that handle inflammation in the brain is the astrocyte, which, upon activation, dramatically increases its production of cytokines and chemokines. Here, we report that NOV/CCN3, added to primary cultured rat brain astrocytes, markedly increased the expression of CCL2 and CXCL1 chemokines, as indicated by ELISA and RT‐qPCR assays. This effect was selective, as the production of thirteen other cytokines and chemokines was not affected by NOV. NOV expression by astrocytes was demonstrated by immunocytochemistry and Western blot analysis, and astrocyte transfection with NOV small interfering RNA (siRNA) markedly decreased CXCL1 and CCL2 production, indicating that endogenous NOV played a major role in the control of astrocytic chemokine synthesis. NOV was shown to mediate several of its actions through integrins. Here, we observed that siRNAs against integrins β1 and β5 decreased basal and abrogated NOV‐stimulated astrocyte expression of CCL2 and CXCL1, respectively. Using a panel of kinase inhibitors, we demonstrated that NOV action on CCL2 and CXCL1 production involved a Rho/ROCK/JNK/NF‐κB and a Rho/qROCK/p38/NF‐κB pathway, respectively. Thus, distinct integrins and signaling mechanisms are involved in NOV‐induced production of CCL2 and CXCL1 in astrocytes. Finally, astrocytic expression of NOV was detected in rat brain tissue sections, and NOV intracerebral injection increased CCL2 and CXCL1 brain levels in vivo. Altogether, our data shed light on the signaling pathways operated by NOV and strongly suggest that NOV mediates astrocyte activation and, therefore, might play a role in neuroinflammation. © 2010 Wiley‐Liss, Inc.
Neural processes for intentional control of perceptual switching: A magnetoencephalography study
Authors: Shimono Masanori , Kitajo Keiichi , Takeda Tsunehiro
Published: June 2010

This article reports an interesting link between the psychophysical property of intentional control of perceptual switching and the underlying neural activities. First, we revealed that the timing of perceptual switching for a dynamical dot quartet can be controlled by the observers' intention, without eye movement. However, there is a clear limitation to this control, such that each animation frame of the stimulus must be presented for a sufficiently long time length; in other words, the frequency of the stimulus alternation must be sufficiently slow for the control. The typical stimulus onset asynchrony for a 50% level of success was about 275 ms for an average of 10 observers. On the basis of psychophysical property, we designed three experiments for investigating the neural process with a magnetoencephalography. They revealed that: (1) a peak component occurring about 300 ms after a reversal was stronger when the direction of perceived motion was switched intentionally than when it was not switched, and (2) neural components about 30–40 ms and 240–250 ms after the reversal of the stimulus animation were stronger when perception was altered intentionally than when it was switched unintentionally. The 300 ms component is consistent with a previous study about passive perceptual switching (Struber and Herrmann [ 2002]: Cogn Brain Res 14:370–382), but the intentional effect was seemed to be a different component from the well‐known P300 component. Hum Brain Mapp, 2011. © 2010 Wiley‐Liss, Inc.
Cognitive impairment and EEG background activity in adults with Down's syndrome: A topographic study
Authors: Velikova Svetla , Magnani Giuseppe , Arcari Claudia , Falautano Monica , Franceschi Massimo , Comi Giancarlo , Leocani Letizia
Published: June 2010

Objective: Studies correlating electroencephalographic (EEG) data and cognitive performance in Down's syndrome (DS) showed conflicting results. The aims of this study were to investigate the sources of EEG rhythms in adults with DS at three dimensional representation of current source density (CSD) using exact/standard Low Resolution Electromagnetic Tomography (e/sLORETA), and their correlation with cognitive performance. Methods: Twenty‐five adults with DS underwent a neuropsychological battery and 5 min of resting, eye‐closed 29‐channel EEG were recorded. After e/sLORETA analysis, data were compared with those from age and gender‐matching control subjects as following: absolute and relative power in delta (1–3 Hz), theta (4–7 Hz), alpha1 (8–9 Hz), alpha2 (10–12 Hz), beta1 (13–18 Hz), beta2 (19–21 Hz), beta3 (22–30 Hz); alpha and theta bands adjusted to individual alpha peak frequency (IAF). Current source activities in DS group in regions showing significant differences compared with controls underwent correlation analysis with psychometric scores. Results: In DS, IAF was shifted to lower frequencies and correlated positively with Wechsler Adult Intelligence Scale and Mini‐Mental State examination. Compared with controls, DS showed increased CSD in: theta, alpha‐1, and beta1 classical bands and in IAF‐adjusted bands, while relative alpha2 was decreased. A negative correlation between cognitive performance and theta/alpha CSD in the right frontal lobe and right posterior cingulate cortex was found. The relative alpha2 correlated positively with cognitive tests. Conclusions: Increased CSD in DS, correlating with cognitive performance, for both slow and fast rhythms suggests involving of cortical and subcortical mechanisms. LORETA might be useful for objective measure of cognitive decline in DS. Hum Brain Mapp, 2011. © 2010 Wiley‐Liss, Inc.
Detection and localization of hippocampal activity using beamformers with MEG: A detailed investigation using simulations and empirical data
Authors: Quraan Maher A. , Moses Sandra N. , Hung Yuwen , Mills Travis , Taylor Margot J.
Published: June 2010

The ability to detect neuronal activity emanating from deep brain structures such as the hippocampus using magnetoencephalography has been debated in the literature. While a significant number of recent publications reported activations from deep brain structures, others reported their inability to detect such activity even when other detection modalities confirmed its presence. In this article, we relied on realistic simulations to show that both sides of this debate are correct and that these findings are reconcilable. We show that the ability to detect such activations in evoked responses depends on the signal strength, the amount of brain noise background, the experimental design parameters, and the methodology used to detect them. Furthermore, we show that small signal strengths require contrasts with control conditions to be detected, particularly in the presence of strong brain noise backgrounds. We focus on one localization technique, the adaptive spatial filter (beamformer), and examine its strengths and weaknesses in reconstructing hippocampal activations, in the presence of other strong brain sources such as visual activations, and compare the performance of the vector and scalar beamformers under such conditions. We show that although a weight‐normalized beamformer combined with a multisphere head model is not biased in the presence of uncorrelated random noise, it can be significantly biased in the presence of correlated brain noise. Furthermore, we show that the vector beamformer performs significantly better than the scalar under such conditions. We corroborate our findings empirically using real data and demonstrate our ability to detect and localize such sources. Hum Brain Mapp, 2011. © 2010 Wiley‐Liss, Inc.
Motor callosal disconnection in early relapsing‐remitting multiple sclerosis
Authors: Wahl Mathias , Hübers Annemarie , Lauterbach‐Soon Birgit , Hattingen Elke , Jung Patrick , Cohen Leonardo G. , Ziemann Ulf
Published: June 2010

In relapsing‐remitting multiple sclerosis (RRMS) the corpus callosum (CC) is often and early affected by macroscopic lesions when investigated by conventional MRI. We sought to determine to which extent microstructural and effective disconnection of the CC are already present in RRMS patients at the earliest stages of the disease prior to evidence of macroscopic CC lesion. We compared 16 very early RRMS patients (median expanded disability status scale (EDSS), 1.5; range, 0–2.0) to an age‐matched group of healthy controls and focused analysis to the motor CC, i.e. that part of the CC relaying interhemispheric motor information. A combined functional magnetic resonance imaging/diffusion tensor imaging fiber‐tracking procedure was applied to identify the callosal motor fibers (CMFs) connecting the hand areas of the primary motor cortices of the two hemispheres. Fractional anisotropy (FA) within the motor CC (FA‐CC) assessed the CMF microstructural integrity. Bifocal paired transcranial magnetic stimulation (TMS) tested short‐interval interhemispheric inhibition (S‐IHI), an established measure of CMF effective connectivity. FA‐CC and S‐IHI were significantly reduced in early RRMS compared to healthy controls. Furthermore, a significant linear correlation between microstructure (FA‐CC) and function (S‐IHI) in the controls was broken down in the patients. These abnormalities were obtained in the absence of macroscopic CMF lesion in conventional MRI, and whilst motor hand/arm function in the nine‐hole‐peg test and corticospinal conduction time were normal. Findings suggest that reductions in FA and S‐IHI may serve as surrogate markers of motor callosal disconnection at the earliest stages of RRMS prior to development of macroscopic lesion. Hum Brain Mapp, 2011. © 2010 Wiley‐Liss, Inc.