bluuebunny/crossref_metadata_2025 huggingface dataset:
Virulence of the entomopathogenic fungusLecanicillium(Deuteromycota: Hyphomycetes) toPissodes strobi(Coleoptera: Curculionidae)
Authors: Kope Harry H. , Alfaro René I. , Lavallée Robert
Published: April 2009

The widely occurring fungal genusLecanicilliumZare & W. Gams (formerlyVerticillium) includes species that are pathogenic to insects. We collected 27Lecanicilliumisolates from soil and from dead adultPissodes strobi(Peck) in British Columbia, Canada, and assessed their virulence against this host. Eighteen isolates were identified asL. longisporum(Petch) Zare & W. Gams and six asL. muscarium(Petch) Zare & W. Gams, while three isolates could not be identified to the species level. We assayed a subset of these isolates (14L. longisporum, 3L. muscarium, and 1Lecanicilliumsp.) as well as the fungal component of the commercial products Mycotal® (L. muscarium) and Vertalec® (L. longisporum) and a herbarium isolate (Lecanicilliumsp.). When adult weevils were inoculated with a conidial suspension (1 × 107conidia/mL), mycosis-related mortality at the end of a 17-day incubation period varied between 20% and 100%, depending on the isolate tested. Eight of the isolates killed >75% of weevils: aLecanicilliumsp. isolate, PFC19, which displayed the lowest LT50value; five indigenousL. longisporumisolates; and both commercial products. In a goodness-of-fit test comparing isolate virulence among species, the unidentified PFC19 isolate was found to be more effective than eitherL. longisporumorL. muscarium, whileL. longisporumcaused somewhat greater mortality thanL. muscarium. In a similar analysis, isolates extracted from soils tended to be more effective than those obtained from cadavers. Horizontal transmission to liveP. strobiwas observed using different isolates ofLecanicilliumspecies. Notwithstanding the variability in virulence, the indigenousLecanicilliumspecies that we isolated and assayed are confirmed as pathogenic toP. strobiin British Columbia.
Euvira micmac, a new species (Coleoptera: Staphylinidae: Aleocharinae), and first record of the genus in Canada
Authors: Klimaszewski Jan , Majka Christopher G.
Published: April 2009

A new aleocharine species,Euvira micmacKlimaszewski and Majka,sp. nov., from Nova Scotia, Canada, is described and illustrated. This is the first record of the genusEuvirafor Canada. New data on bionomics and distribution are provided, including notes on the red oak gall environment where the species was found. A short diagnosis, description, colour habitus image, and black and white genital images are provided. The lectotype (male) and the paralectotypes (5 females) are designated forE. quadriceps(Casey). Two beetles,Litargus tetraspilotusLeConte (Mycetophagidae) andMelanophthalma americana(Mannerheim) (Latridiidae), found co-inhabiting red oak galls are newly recorded for Atlantic Canada.
Effect of melanism of alpine Colias nastes butterflies (Lepidoptera: Pieridae) on activity and predation
Authors: Roland Jens
Published: April 2009

Melanism in the sulphur butterfly Colias nastes Boisduval was quantified and related to their ability to remain active under cool or cloudy conditions and to their risk of predation. Darker individuals were more active, moved greater distances, and disappeared from the population at a greater rate. Disappearance of darker individuals was not due to greater predation. Light-coloured individuals suffered greater predation than dark individuals, but only at higher elevations. The broad geographical pattern of increased melanism in Arctic and alpine Colias butterflies is likely a response to the consistent pattern of cooler temperatures in these habitats rather than local variation in predation pressure.
Field evaluation of host kairomones and pheromones for capture of Conophthorus coniperda (Coleoptera: Scolytidae)
Authors: Brauner A.M. , de Groot P.
Published: April 2009

Field studies were conducted to determine the attractiveness of monoterpenes and pheromones to the white pine cone beetle, Conophthorus coniperda (Schwarz), the most destructive cone and seed pest of eastern white pine, Pinus strobus L. (Pinaceae). Limonene was identified as a new attractant that acts synergistically when added to the female-produced sex pheromone, pityol. Trap catches were higher with increasing release rates of S-(–)-limonene. The enantiomers of limonene showed equivalent efficacy on mean trap catch. (–)-β-Pinene was not attractive and may be repellent to both sexes, and (–)-α-pinene was shown to have no effect on female response when added to pityol or pityol + S-(–)-limonene. The pheromones trans-verbenol, trans-pinocarveol, and myrtenol were not attractive to C. coniperda.
Effect of small-scale forest management on fungivorous Coleoptera in old-growth forest fragments in southeastern Ontario, Canada
Authors: Zeran Rebecca M. , Anderson Robert S. , Wheeler Terry A.
Published: April 2009

Fungivorous Coleoptera were sampled from old-growth and managed (selectively logged in 1999) hemlock–hardwood forests in southeastern Ontario to examine the effect of small-scale forest management on fungivore diversity in forest fragments. Sampling using flight-intercept traps and trunk-window traps for 22 weeks in 2003 yielded 11 888 beetles representing 73 species in 11 target families (Anthribidae, Cerylonidae, Endomychidae, Erotylidae, Leiodidae, Mycetophagidae, Scaphidiidae, Sphindidae, Tenebrionidae, Trogossitidae, and Zopheridae). The leiodid subfamily Leiodinae was the dominant taxon (10 386 individuals, 38 species). While old-growth stands had no recent logging and had higher volumes of coarse woody debris, species diversity and composition of fungivorous Coleoptera were similar between forest types, suggesting that the stand differences measured (recent logging history, volume of coarse woody debris) did not have a significant effect on beetle diversity in this study. Indicator species analysis showed that Triplax macra LeConte (Erotylidae) was strongly associated with old-growth stands, while Anisotoma blanchardi (Horn), Anogdus obsoletus (Melsheimer), Agathidium sp. 1 (Leiodidae), and Mycetina perpulchra (Newman) (Endomychidae) were associated with managed stands. The lack of difference observed between stand types may be related to the small size of the forest fragments or the relatively small scale of the disturbance.
Suitability ofAcer saccharumandAcer pensylvanicum(Aceraceae) for rearingAnoplophora glabripennis(Coleoptera: Cerambycidae)
Authors: Hajek Ann E. , Kalb David M.
Published: April 2009

Striped maple (Acer pensylvanicumL.) was compared with sugar maple (Acer saccharumMarsh.) for use in rearing Asian longhorned beetles (Anoplophora glabripennis(Motschulsky)). Adult females lived longer when caged with twigs and small bolts harvested fromA. pensylvanicumduring late spring through early fall than with material fromA. saccharumcollected at the same time. Females had a shorter life-span when fed plant material from either tree species harvested from late fall through winter than with plant material fromA. pensylvanicumharvested from late spring through early fall. FemaleA. glabripennislaid more viable eggs when provided withA. pensylvanicumrather thanA. saccharum. Regardless of which of these two tree species females had experienced previously, they always chose to lay more eggs inA. pensylvanicumthan inA. saccharum. RearingA. glabripennisonA. pensylvanicumis therefore more efficient, especially when twigs and wood collected from late spring through early fall are used.
Biodiversity of ground beetles (Coleoptera: Carabidae) and spiders (Araneae) across a tallgrass prairie – aspen forest ecotone in southern Manitoba
Authors: Roughley Robert E. , Pollock Darren A. , Wade David J.
Published: April 2009

The objective of this study was to assess the similarities and differences between selected bioindicator groups within tallgrass prairie and adjacent aspen forest. Based on pitfall trapping from 1998 to 2000, species richness and abundance of ground beetles and spiders were examined across a tallgrass prairie – aspen forest ecotone located near Winnipeg, Manitoba. The abundance of spiders and ground beetles was higher in the forested portion of the transect than in the prairie section. There were 639 specimens of ground beetles collected, representing 53 species; 19 species were found only on the prairie, 19 species were found only in the forest, and 15 species were found in both habitats, although the abundance of most species was too low to confidently assign them to either habitat type. Excluding single records in any sampling year yielded 9 prairie species, 5 forest species, and 10 species found in both aspen forest and tallgrass prairie. The five most abundant species of ground beetles were Agonum placidum (Say), Pterostichus caudicalis (Say), P. femoralis (Kirby), P. melanarius (Illiger), and Synuchus impunctatus (Say). There were 4499 specimens of spiders collected, representing 92 species; 25 species were found only in the prairie, 15 species were unique to the aspen forest, and 52 species were found in both habitats. Excluding single records in any sampling year yielded 26 prairie species, 15 forest species, and 22 species found in both habitats. The five most abundant species of spiders were Pardosa moesta Banks, P. distincta (Blackwall), Agroeca ornata Banks, Centromerus sylvaticus (Blackwall), and Alopecosa aculeata (Clerck). Our study concurs with other studies in demonstrating that there are distinct assemblages of both groups of predators in each of the two habitat types.
Variation in CanadianGomphus fraternus(Odonata: Gomphidae) in relation to the recognition of subspeciesmanitobanus
Authors: Catling Paul M. , Hughes Marjorie
Published: April 2009

Seven characters were evaluated in 146 specimens ofGomphus fraternus(Say), including both subspecies,G. f. fraternus(Say) andG. f. manitobanusWalker, to clarify their circumscription and geographic occurrence in Canada. Specimens corresponding to subspeciesmanitobanuswere all from the Assiniboine and Red rivers and formed a discrete group in a principal components analysis, supporting their taxonomic recognition. Their distribution in Canada suggests a separation of subspecies near the boundary of the prairie ecozone in central southern Manitoba. In subspeciesfraternusthe extensor surfaces of the tibiae are largely black, with pale areas often lacking and rarely up to 50% of the segment length. Similarly the dorsal surface of abdominal segment 9 is largely black. If there is a pale area, it is <1 mm long. In subspeciesmanitobanusthe extensor surfaces of the tibiae have pale markings on ≥50% of their lengths and the dorsal surface of abdominal segment 9 has a dorsal yellow spot ≥1.4 mm long. Widespread dragonflies in western North America are paler in drier climates and the increased pale colouration in the western subspeciesmanitobanuscorresponds to this trend. Currently known only from Manitoba, subspeciesmanitobanusmay occur in prairie habitats of the Midwestern United States, based on reports of pale individuals in that region.
Six new species and records of aleocharine beetles from the Yukon and Alaska (Coleoptera: Staphylinidae: Aleocharinae)
Authors: Klimaszewski Jan , Godin Benoit , Pelletier Georges , Savard Karine
Published: April 2009

Six new aleocharine species are described and illustrated from the Yukon and Alaska: Atheta (Dimetrota) cadeti Klimaszewski and Godin, sp. nov.; Atheta (Hypatheta) pseudomet lakatlana Klimaszewski and Godin, sp. nov.; Cypha inexpectata Klimaszewski and Godin, sp. nov.; Oxypoda yukonensis Klimaszewski and Godin, sp. nov., Oxypoda pseudoconvergens Klimaszewski and Godin, sp. nov.; and Clusiota antennalis Klimaszewski and Godin, sp. nov.Atheta (Rhagocneme) subsinuata (Erichson), known from the western Palaearctic region, was discovered in the Yukon and is reported in North America for the first time as an adventive species. Amischa tersa Casey is recorded from Canada and the Yukon for the first time. Twenty-four new records of aleocharine species from the Yukon are provided in addition to species described as new to science. One hundred and fifteen digital images of external and genital structures are provided for species identification.
Bumble bees influence berry size in commercialVacciniumspp. cultivation in British Columbia
Authors: Ratti Claudia M. , Higo Heather A. , Griswold Terry L. , Winston Mark L.
Published: April 2009

We studied the abundance, diversity, and dispersion patterns of managed and wild bee (Hymenoptera: Apoidea) populations in commercial highbush blueberry and cranberry (Ericaceae:Vaccinium corymbosumL.,Vaccinium macrocarponAit.) fields in the Fraser Valley of British Columbia, and assessed their potential as pollinators of these crops by determining which groups of bees had the greatest impact on percent yield and mass of berries. Bumble bees were evenly distributed within both crops. Other wild bee species were well distributed in blueberry fields but generally remained at edges of cranberry fields. Percent berry yield was not related to bee abundance for any group of bees, nor was species diversity correlated with berry mass. Blueberry mass and cranberry mass were related to abundance of bumble bees but not to that of honey bees or other wild bees. Bumble bees are recommended as potential alternative pollinators of these crops.
Evidence of a female sex pheromone in Bradysia odoriphaga (Diptera: Sciaridae)
Authors: Li Hong-Jun , He Xiong-Kui , Zeng Ai-Jun , Liu Ya-Jia , Jiang Shu-Ren
Published: April 2009

The existence of a sex pheromone of Bradysia odoriphaga Yang and Zhang was investigated prior to the possible development of a semiochemical-based monitoring system or tools for controlling this pest. In laboratory bioassays, live virgin females stimulated 91% of males to attempt to mate. Methylene dichloride washes of whole bodies and excised ovipositors of females attracted males in olfactometer assays. These results indicate the presence of a female sex pheromone in B. odoriphaga, with the ovipositor as its possible source.
Composition of spider prey captured by the waspTrypoxylon(Trypargilum)tridentatum tridentatumin two habitats in an oasis in Baja California Sur, Mexico
Authors: Domínguez Karina , Jiménez María Luisa
Published: April 2009

Trypoxylon(Trypargilum)tridentatum tridentatumPackard (Hymenoptera: Crabronidae) is a spider-hunting wasp in mesic and xeric habitats in the arid Baja California peninsula of Mexico. Spider (Araneae) prey were collected every 2 weeks from wasp trap nests. Individuals of the family Araneidae were the most abundant prey (60.9%), followed by Theridiidae and Mimetidae. Dictynidae, Anyphaenidae, Salticidae, Uloboridae, Tetragnathidae, Miturgidae, and Philodromidae were captured only in the mesic habitat. An unidentified species ofEriophoraSimon (Araneidae) was the most frequently collected spider in the xeric habitat (29.0%), followed byTheridion submissumGertsch and Davis (Theridiidae) (24.0%), which was the commonest prey species in the mesic habitat (21.1%), andMetepeira crassipesChamberlin and Ivie (Araneidae) (16.5%). Nineteen species and three families are newly recorded as prey. The araneidsAraneus lineatipes(O.P.-Cambridge) andKaira alba(Hentz) and the uloboridsPhiloponella arizonica(Gertsch) andUloborus segregatusGertsch are new records for Baja California.
Efficiency of a herbivore–plant interaction: conversion of biomass from flax (Linaceae) to aphid, Macrosiphum euphorbiae (Hemiptera: Aphididae)
Authors: Lamb Robert J. , Grenkow Larry
Published: April 2009

The specific impact of the aphid Macrosiphum euphorbiae (Thomas) on seedlings of common flax, Linum usitatissimum L., is 3.317 mg/mg, quantified as the dry mass of plant tissue required to produce a unit of herbivore tissue. This measure of the efficiency of biomass conversion between trophic levels for the aphid–flax interaction is similar to that previously reported for seven species of aphid on monocotyledonous cereals (Poaceae), but lower than that for two species of aphid on a species of Brassicaceae, a dicotyledonous plant. Therefore, the interaction between M. euphorbiae and the dicot, flax, does not support the hypothesis that aphids have less impact on monocots than on dicots.
A technique for transplanting gall-making insects: impacts on gall-maker and parasitoid larvae
Authors: Cox Graham H. , Heard Stephen B. , Seehawer Julie M.
Published: April 2009

Past studies of gall-maker-host interactions have been hampered by an inability to conduct experimental transplants of individuals between host plants. We describe a method for transplanting gall-maker larvae between galls on different individual host plants. Our method involves removing and inserting larvae through slits cut in young galls, and allows for healing and continuing growth of the gall. We developed and tested our method with larvae of the gall-making moth Gnorimoschema gallaesolidaginis Riley (Lepidoptera: Gelechiidae) on its two host plants, Solidago altissima L. and S. gigantea Ait. (Asteraceae). For three of four host × year combinations, unparasitized larvae survived at similar rates in transplants and controls. On one host in one year, transplant survival was low, possibly as a result of severe drought stress. Interestingly, survival of parasitized gall-maker larvae was lower in transplants for three of four host × year combinations, suggesting that gall-makers stressed by parasitoid attack are less able to tolerate transplant stress. Our technique may be applicable to many other gall-maker species, especially those making relatively thin-walled galls, and should represent a valuable new tool for the study of gall-maker-host interactions.
Determinants of adherence to antiretroviral drugs among people living with HIV/AIDS in the Ife-Ijesa zone of Osun state, Nigeria
Authors: Afolabi Muhammed O. , Ijadunola Kayode T. , Fatusi Adesegun O. , Olasode Olayinka A.
Published: April 2009

Background: The advent of antiretroviral (ARV) drugs has transformed HIV/AIDS into a chronic manageable disease and strict adherence is required for the medication to be effective. However, factors influencing adherence to ARV therapy (ART) vary from country to country.Method: 120 subjects who received ARV drugs at a federal government-designated ART site located within the Obafemi Awolowo University Teaching Hospital complex, (OAUTHC), Ile-Ife, and a community-based non-governmental organisation, Living Hope Care (LIHOC), Ilesa, from February to May 2006 were serially recruited and studied. Relevant data were collected using an interviewer-administered, patient medication adherence questionnaire. Focus group discussions were also held among the subjects to further elicit qualitative information on factors influencing adherence to ART.Results: The age of participants ranged from 21 to 65 years with a mean age of 40.2 + 10.3 years. Participants had been on ARV drugs for a period ranging between three and 60 months. The overall adherence rate in the study population was 44%. 66% of participants who accessed ARV drugs from LIHOC, Ilesa, had good adherence while only 14% of participants who accessed ARV drugs from OAUTHC, Ile-Ife, had good adherence. Participants with good adherence did not pay funds for the preliminary ARV eligibility investigations and they were also offered regular adherence counselling. These facilities were barely available in the group with poor adherence. Demographic factors such as age, gender and marital status did not seem to have any significant association with adherence level (p > 0.05).Conclusion: The level of adherence was high in a cohort of PLWHA accessing ARV drugs in Ilesa while it was low among PLWHA receiving ART in Ife. The most important reasons for this difference were lack of funds for investigations and poor psycho-social counselling.
Titelbild: Direct CH Metalation with Chromium(II) and Iron(II): Transition‐Metal Host / Benzenediide Guest Magnetic Inverse‐Crown Complexes (Angew. Chem. 18/2009)
Authors: Alborés Pablo , Carrella Luca M. , Clegg William , García‐Álvarez Pablo , Kennedy Alan R. , Klett Jan , Mulvey Robert E. , Rentschler Eva , Russo Luca
Published: April 2009

Chrom und Eisen als die neuesten Ergänzungen des Konzepts der alkalimetallvermittelten Metallierung stellen J. Klett, R. E. Mulvey et al. in ihrer Zuschrift auf S. 3367 ff. vor. Das elektropositivere Natrium ist wesentlich für die Reaktion, doch das weniger elektropositive Chrom oder Eisen ist es, das Benzol tatsächlich deprotoniert. Diese neuartige Reaktivität kann mit einem Schachspiel verglichen werden, bei dem die Königin (Na) dem König Schach bietet und der Springer (Cr, Fe) Matt setzt.

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Inside Cover: Intermolecular Methoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II) Bis(oxazoline) Complexes (Angew. Chem. Int. Ed. 18/2009)
Authors: Kato Keisuke , Motodate Satoshi , Mochida Tomoyuki , Kobayashi Takuya , Akita Hiroyuki
Published: April 2009

Ein Bisoxazolin‐Ligand erhöht die Präferenz von PdII für π‐Systeme. Die direkte Umwandlung von terminalen Alkinen in β‐Methoxyacrylate mit Komplexen solcher Bisoxazolin(box)‐Liganden wird von K. Kato und Mitarbeitern in der Zuschrift auf S. 3326 ff. beschrieben. Dichtefunktionalrechnungen belegen, dass die π‐Orbitale des Liganden in [Pd(box)(TFA)2] über die Doppelbindungen und die Peripherie delokalisiert sind und energetisch nahe dem LUMO liegen. Die Reaktion kann auch in einer Synthese von Kawain genutzt werden.

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Water‐soluble 3,4:9,10‐perylene tetracarboxylic ammonium as a high‐performance fluorochrome for living cells staining
Authors: Zhao Yingjie , Zhang Xin , Li Dianqing , Liu Daicheng , Jiang Wenfeng , Han Cixiang , Shi Zhiqiang
Published: April 2009

Highly water‐soluble 3,4:9,10‐perylene tetracarboxylic ammonium with quantitative fluorescence quantum yield was designed. Owing to the high negative electrostatic potential of the perylene plane, the perylene dye remained stable over a broad pH range and was successfully applied as a high‐performance fluorochrome for living hippocampal neurons staining. Copyright © 2009 John Wiley & Sons, Ltd.
A novel gaseous dimethylamine sensor utilizing cataluminescence on zirconia nanoparticles
Authors: Yu Chao , Liu Guohong , Zuo Boli , Tang Rongjun
Published: April 2009

A novel cataluminescence (CTL) sensor using ZrO2 nanoparticles as the sensing material was developed for the determination of trace dimethylamine in air samples based on the catalytic chemiluminescence (CL) of dimethylamine on the surface of ZrO2 nanoparticles. The CTL characteristics and the different factors on the signal intensity for the sensor, including nanomaterials, working temperature, wavelength and airflow rate, were investigated in detail. The CL intensity on ZrO2 nanoparticles was the strongest among the seven examined catalysts. This novel CL sensor showed high sensitivity and selectivity to gaseous dimethylamine at optimal temperature of 330°C. Quantitative analysis was performed at a wavelength of 620 nm. The linear range of CTL intensity vs concentration of gaseous dimethylamine was 4.71 × 10−3 to 7.07 × 10−2 mg L−1 (r = 0.9928) with a detection limit (3σ) of 6.47 × 10−4 mg L−1. No or only very low levels of interference were observed while the foreign substances such as benzene, hydrochloric acid, methylbenzene, chloroform, n‐hexane and water vapor were passing through the sensor. The response time of the sensor was less than 50 s, and the sensor had a long lifetime of more than 60 h. The sensor was successfully applied to the determination of dimethylamine in artificial air samples, and could potentially be applied to analysis of nerve agents such as Tabun (GA). Copyright © 2009 John Wiley & Sons, Ltd.
Quantification of global DNA methylation with infrared fluorescence in liver and muscle tissues of differentially fed boars
Authors: Braunschweig Martin H.
Published: April 2009

Methylation of cytosine residues at CpG sites is involved in various biological processes to control gene regulation and gene expression. Global DNA methylation is changed in different tumors and in cloned animals. Global DNA methylation can be accurately quantified by dot blot analysis with infrared (IR) fluorophores. Methylated lambda DNA was used as model DNA to develop and validate an immunochemical assay with IR fluorescence detection. Two different IR fluorophores were used, one to detect 5‐methylcytosine and another to account for DNA loading. A sensitive infrared detection method was established which is suitable for accurate and reproducible quantification of global DNA methylation across a wide dynamic range. This method was subsequently employed to quantify global DNA methylation in liver and in muscle tissues of boars which have received either a control diet or a methyl supplemented diet in an ongoing study. A significant difference in global DNA methylation is indicated in muscle but not in liver tissue between the two groups of boars. Copyright © 2009 John Wiley & Sons, Ltd.
Liquid chromatographic determination of acetylcholine based on pre‐column alkaline cleavage reaction and post‐column tris(2,2′‐bipyridyl)ruthenium(III) chemiluminescence detection
Authors: Yoshida Hideyuki , Yamada Akifumi , Todoroki Kenichiro , Imakyure Osamu , Nohta Hitoshi , Yamaguchi Masatoshi
Published: April 2009

A method for the determination of acetylcholine (ACh) has been developed using liquid chromatography with chemiluminescence detection. This method is based on the pre‐column alkaline cleavage of ACh to form trimethylamine (TMA) and the post‐column tris(2,2′‐bipyridyl)ruthenium(III) chemiluminescence detection of TMA. ACh was converted to TMA with high yield at 180°C in the presence of lithium hydroxide, and the produced TMA was separated on a cation‐exchange/reversed‐phase dual‐functional column using a mixture of 0.2 m potassium phosphate buffer (pH 5.9) and acetonitrile (20:1, v/v) as the mobile phase. The eluate was online mixed with acidic tris(2,2′‐bipyridyl)ruthenium(III) solution, and the generated chemiluminescence was detected. The detection limit (signal‐to‐noise ratio = 3) for ACh was 0.80 nmol/mL, which corresponded to 1.1 pmol TMA per injection volume of 5 µL. This is simple and robust method that does not need an expensive device and unstable enzymes, and was applied to the determination of ACh in pharmaceutical formulations. Copyright © 2009 John Wiley & Sons, Ltd.
The assaying of haemoglobin using luminol chemiluminescence and its application to the dating of human skeletal remains
Authors: Creamer J. I. , Buck A. M.
Published: April 2009

The luminol chemiluminescence reaction has, for some time, been used as a tool for the detection of haemoglobin at crime scenes. More recently, the luminol test has been suggested as a possible tool for estimating the post‐mortem interval (PMI) of skeletal remains. The preliminary results from the following study indicate that the chemiluminescent luminol test is a relatively easy and economical method for distinguishing between remains of medico‐legal (≤100 years) and historical (>100 years) interest. The femur was the preferred bone for PMI measurements using the luminol test, due to its robustness and relative resistance to diagenesis. Initial results suggest that bone that was historical in nature, produced a demonstrably weaker reaction than that of medico‐legal interest. These results suggest that the luminol test is a promising technique, albeit with some limitations, for the assessment of skeletal material that may be potentially of medico‐legal interest. Copyright © 2009 John Wiley & Sons, Ltd.
Directed evolution of a Bacillus chitinase
Authors: Songsiriritthigul Chomphunuch , Pesatcha Putarika , Eijsink Vincent G.H. , Yamabhai Montarop
Published: April 2009

Chitinases have potential in various industrial applications including bioconversion of chitin waste from crustacean shells into chito‐oligosaccharide‐based value‐added products. For industrial applications, obtaining suitable chitinases for efficient bioconversion processes will be beneficial. In this study, we established a straightforward directed evolution method for creating chitinase variants with improved properties. A library of mutant chitinases was constructed by error‐prone PCR and DNA shuffling of two highly similar (99% identical) chitinase genes from Bacillus licheniformis. Activity screening was done in two steps: first, activity towards colloidal chitin was screened for on culturing plates (halo formation). This was followed by screening activity towards the chitotriose analogue p‐nitrophenyl‐β‐1,4‐N, N'‐diacetyl‐chitobiose at various pH in microtiter plates. From a medium‐throughput screening (517 colonies), we were able to isolate one mutant that demonstrated improved catalytic activity. When using p‐nitrophenyl‐β‐1,4‐N, N'‐diacetyl‐chitobiose as substrate, the overall catalytic efficiency, kcat/Km of the improved chitinase was 2.7‐ and 2.3‐fold higher than the average kcat/Km of wild types at pH 3.0 and 6.0, respectively. The mutant contained four residues that did not occur in either of the wild types. The approach presented here can easily be adopted for directed evolution of suitable chitinases for various applications.
Systemic lupus erythematosus and C1q: A quantitative ELISA for determining C1q levels in serum
Authors: Dillon Skyler P. , D'Souza Anil , Kurien Biji T. , Scofield R. Hal
Published: April 2009

C1q is of interest in systemic lupus erythematosus (SLE) research due to deficiencies in its activity being associated with the disease. Current published protocols for measuring C1q vary greatly in their results and ease of reproducibility. Due to this, average C1q concentrations have been reported between 56 and 276 μg/mL in non‐SLE serum. We present an improved method for quantifying C1q concentrations, which employs a sandwich ELISA. This method has improved precision, cost efficiency, up‐scaling, reproducibility, and uses significantly lesser volumes of serum sample when compared to RID and other methods for quantifying C1q. We report an average concentration of 113 ± 40 μg/mL for C1q in non‐SLE serum. The assay designed here will be useful in the high‐throughput measurement of serum C1q in SLE cases.
Meeting report: Protein Design and Evolution for Biocatalysis
Authors: Bornscheuer Uwe
Published: April 2009

October 25th–30th, 2008, Sant Feliu de Guixols, Spain
Ribosomal Synthesis of Peptides with C‐Terminal Lactams, Thiolactones, and Alkylamides
Authors: Nakajima Eiji , Goto Yuki , Sako Yusuke , Murakami Hiroshi , Suga Hiroaki
Published: April 2009

All change at the C terminus: We have established a novel methodology for the ribosomal synthesis of peptides featuring C‐terminal cyclization and various modifications, including macrocyclization, by making use of genetic code reprogramming. The C‐terminal amide modification of linear and cyclic peptides should enhance their physiological stabilities, and open up the possibility of developing new drug‐like peptides.

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The C terminus of a peptide expressed by the translation apparatus generally ends in a carboxylate group. On the other hand, the C termini of some naturally occurring peptides have amide moieties instead of carboxylates, which are believed to give better biostability. Here, we describe a new strategy for the ribosomal synthesis of peptides featuring C‐terminal lactam, thiolactone, and alkylamide units. The method was based on the concept of genetic code reprogramming involving the flexizymes (flexible tRNA acylation ribozymes) and the PURE (peptide synthesis using recombinant elements) system, in which vacant codons are reassigned to nonproteinogenic amino acids; this enabled us to convert the C termini of peptides into the above functionalities. We have also applied this method to the synthesis of a macrocyclic peptide closed by an amide bond formed between a lysine side chain and the peptide C terminus. This method thus offers us new opportunities to express various peptides with C‐terminal modifications as well as macrocyclic peptides using the translation apparatus, and potentially to accelerate the discovery of peptidic drugs designed for various therapeutic targets.
Design, Synthesis, and Biological Evaluation of Artificial Macrosphelides in the Search for New Apoptosis‐Inducing Agents
Authors: Matsuya Yuji , Kobayashi Yuta , Kawaguchi Takanori , Hori Ayana , Watanabe Yuka , Ishihara Kentaro , Ahmed Kanwal , Wei Zheng‐Li , Yu Da‐Yong , Zhao Qing‐Li , Kondo Takashi , Nemoto Hideo
Published: April 2009

A drug of two halves: New artificial compounds composed of a macrosphelide core skeleton and an epothilone side chain were designed and synthesized. These compounds were more potent inducers of apoptosis than the parent natural‐type macrosphelides.

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Various artificial macrosphelides were designed and synthesized, including ring‐enlarged analogues and epothilone‐hybrid compounds. Syntheses were accomplished in an efficient manner by using a ring‐closing metathesis (RCM) strategy in a key macrocyclization step. Biological evaluation of these new macrosphelide‐based derivatives revealed that several epothilone hybrids, in which a thiazole‐containing side chain was incorporated, exhibited potent apoptosis‐inducing activity toward human lymphoma cells. These activities were considerably enhanced relative to those of natural macrosphelide compounds. Structure–activity relationship studies revealed that the “ene‐dicarbonyl” substructure is apparently essential for bioactivity.
Design of and Mechanistic Studies on a Biomimetic Iron–Imidazole Catalyst System for Epoxidation of Olefins with Hydrogen Peroxide
Authors: Schröder Kristin , Enthaler Stephan , Bitterlich Bianca , Schulz Thomas , Spannenberg Anke , Tse Man Kin , Junge Kathrin , Beller Matthias
Published: April 2009

One step further in bio‐inspired catalytic epoxidation reactions was made in investigations on iron/imidazole catalyst systems (see the crystal of one example) with hydrogen peroxide as the terminal oxidant, in which it was shown for the first time that defined iron–imidazole complexes are capable of epoxidizing challenging aliphatic olefins. X‐ray studies, UV/Vis titrations, and NMR studies were carried out to clarify the mechanism.

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Novel iron catalysts, both defined and in situ generated, for the epoxidation of aromatic and aliphatic olefins with hydrogen peroxide as terminal oxidant are described. Our catalyst approach is based on bio‐inspired 1‐aryl‐substituted imidazoles in combination with cheap and abundant iron trichloride hexahydrate. We show that the free 2‐position of the imidazole ligand motif plays a key role for catalytic activity, as substitution leads to a dramatic depletion of yield and conversion. X‐ray studies, UV/Vis titrations, and NMR studies were carried out to clarify the mechanism.
Cover Picture: Solid‐State Structural Characterization of Cutinase–ECE‐Pincer–Metal Hybrids (Chem. Eur. J. 17/2009)
Authors: Rutten Lucy , Wieczorek Birgit , Mannie Jean‐Paul B. A. , Kruithof Cornelis A. , Dijkstra Harm P. , Egmond Maarten R. , Lutz Martin , Klein Gebbink Robertus J. M. , Gros Piet , van Koten Gerard
Published: April 2009

The interfacial enzyme cutinase…︁ shown at the air–water interface on the cover, was site‐selectively modified with two different ECE‐pincer–metal complexes. The resulting cutinase–pincer–metal hybrids crystallized under halide‐rich conditions to give monomeric crystal structures, but also crystallized under halide‐poor conditions to form a metal‐induced dimer. See the Full Paper by R. J. M. Klein Gebbink, P. Gros, G. van Koten et al. on page 4270 ff., for details of the chemistry and the crystal structures. Photograph: View from the island of Saba (Netherlands Antilles) taken by Birgit Wieczorek. Design: Birgit Wieczorek and Cornelis A. Kruithof.

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Conversion of Furfuryl Alcohol into Ethyl Levulinate using Solid Acid Catalysts
Authors: Lange Jean‐Paul , van de Graaf Wouter D. , Haan René J.
Published: April 2009

Cellulosic biofuel: Ethyl levulinate is a promising biofuel that can be obtained from lignocellulosic residues. A byproducts, furfural, can be converted into ethyl levulinate in an acid‐based process. Here, the use of solid acid catalysts for the conversion of furfuryl alcohol into ethyl levulinate is reported.

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Furfural, a potential coproduct of levulinic acid, can be converted into levulinic acid via hydrogenation to furfuryl alcohol and subsequent ethanolysis to ethyl levulinate. The ethanolysis reaction is known to proceed in the presence of H2SO4. We show here that several strongly acidic resins are comparably effective catalysts for this reaction. Optimal performance is achieved by balancing the number of acid sites with their accessibility in the resin. Acidic zeolites such as H‐ZSM‐5 also catalyze this reaction, although with a lower activity and a higher coproduction of diethyl ether.
Utility of HoxB2 enhancer‐mediated Cre activity for functional studies in the developing inner ear
Authors: Szeto Irene Y.Y. , Leung Keith K.H. , Sham Mai Har , Cheah Kathryn S.E.
Published: April 2009

The rhombomere 4(r4)‐restricted expression of the mouse Hoxb2 gene is regulated by a 1.4‐kb enhancer‐containing fragment. Here, we showthat transgenic mouse lines expressing cre driven by this fragment (B2‐r4‐Cre), activated the R26R Cre reporter in rhombomere 4 and the second branchial arch, the epithelium of the first branchial arch, apical ectodermal ridge of the limb buds and the tail region. Of particular interest is Cre activity in the developing inner ear. Cre activity was found in the preotic field and otic placode at E8.5 and otocyst at E9.5–E12.5, in the cochleovestibular and facio‐acoustic ganglia at E10.5 and the vestibular and spiral ganglia and all the otic epithelia derived from the otocyst at E15.5 and P0. Our data suggest that the B2‐r4‐Cre transgenic mice provide an important tool for conditional gene manipulation and lineage tracing in the inner ear. In combination with other transgenic lines expressing cre exclusively in the otic vesicle, the relative contributions of the hindbrain, periotic mesenchyme and otic epithelium in otic development can be dissected. genesis 47:361–365, 2009. © 2009 Wiley‐Liss, Inc.
Synthesis and in vitro Efficacy Studies of Silver Carbene Complexes on Biosafety Level 3 Bacteria
Authors: Panzner Matthew J. , Deeraksa Arpaporn , Smith Alyssa , Wright Brian D. , Hindi Khadijah M. , Kascatan‐Nebioglu Aysegul , Torres Alfredo G. , Judy Barbara M. , Hovis Christine E. , Hilliard Julia K. , Mallett Rebekah J. , Cope Emily , Estes D. Mark , Cannon Carolyn L. , Leid Jeff G. , Youngs Wiley J.
Published: April 2009

A series of N‐heterocyclic carbene silver complexes have been synthesized and tested against the select group of biosafety level 3 bacteria Burkholderia pseudomallei, Burkholderia mallei, Bacillus anthracis, methicillin‐resistant Staphylococcus aureus and Yersinia pestis. Minimal inhibitory concentrations, minimal bactericidal and killing assays demonstrated the exceptional efficacy of the complexes against these potentially weaponizable pathogens. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Transition States of the Asymmetric Michael Reactions of Aldehydes Catalyzed by Trimethylsilyl‐Protected Diphenylprolinol
Authors: Zhao Jian‐Qiang , Gan Li‐Hua
Published: April 2009

The asymmetric Michael reactions of aldehydes and nitroalkenes catalyzed by trimethylsilyl‐protected diphenylprolinol were investigated by using density functional theory calculations. As a result of the stereospecific blockade of the bulky diphenylsiloxymethyl group on the pyrrolidine ring, the Re face of the enamine double bond is effectively shielded. For acetaldehyde, there are two different conformers of the enamine intermediate. On the basis of the two conformers of the enamine intermediate, four different reaction pathways were considered and four different transition states were searched for the enantioselective asymmetric Michael reaction of acetaldehyde and nitroalkene. The lowest‐ and second‐lowest‐energy transition states are both formed via the same intermediate IM2. The enantiomeric excess, calculated to be 96 % ee, is in good agreement with the experimental value. For propanal, on the basis of the four different conformers of the prolinol–enamine intermediate, eight different reaction pathways were considered and eight transition states were searched for the enantioselective asymmetric Michael reaction. The calculated ee value is 99.5 %, which is in good agreement with the experimental ee value of 99 %. The lowest‐ and second‐lowest‐energy transition states are formed via different enamine intermediates, which is different from the case of acetaldehyde. The calculations also reveal that the intermediates play an important role in the reactions.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Synthesis of New Analogues of the Tetraponerines
Authors: Rouchaud Anne , Braekman Jean‐Claude
Published: April 2009

To evaluate the influences of the tetraponerine alkyl chains and tricyclic ring systems on their cytotoxic activities, we have prepared a series of alkyl derivatives (3a, 3b and 4a–f) of the non‐natural tricyclic skeletons decahydro‐2H,6H‐dipyrido[1,2‐a:1′,2′‐c]pyrimidine (3, 6–6–6 skeleton) and dodecahydro‐2H‐1,8a‐diazaphenanthrene (4, iso‐6–6–6 skeleton). In this study, two ways to synthesise the 6–6–6 analogues have been developed and compared. One is based on the condensation of α‐tripiperideine with diethyl malonate (DEM) in water at pH 11. This yielded oxo ester 11, precursor of the amino nitrile 8, but only in moderate yield. In the second pathway, the key intermediate 8 was more efficiently synthesised by starting from 2‐(2‐piperidyl)ethanol. Treatment of 8 with alkyl Grignard reagents led to the 6–6–6 analogues 3a and 3b. When the one‐pot reaction between α‐tripiperideine and DEM was performed in water at pH 8, the lactam 12, precursor of the iso‐6–6–6 skeleton, was obtained in a yield of 76 %. The same lactam was also obtained in a yield of 86 % by treatment of tetrahydroanabasine 14 with DEM in water at pH 8. Lactam 12 was transformed into the iso‐6–6–6 analogues 4a–4f. The cytotoxic activities of the 6–6–6 and iso‐6–6–6 analogues against HT29 cancer cells were compared with those of the 5–6–5 and 6–6–5 tetraponerines and with those of solenopsin analogues. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Facile Access to Bicyclic Sultams with Methyl 1‐Sulfonylcyclopropane‐1‐carboxylate Moieties
Authors: Rassadin Valentin A. , Tomashevskiy Aleksandr A. , Sokolov Viktor V. , Ringe Arne , Magull Jörg , de Meijere Armin
Published: April 2009

N‐(2,3‐Dibromopropyl)‐ and N‐(3,4‐dibromobutyl)(methoxycarbonyl)methanesulfanilides upon treatment with potassium carbonate in DMF furnish methyl 3‐aryl‐2,2‐dioxo‐2‐thia‐3‐azabicyclo[n.1.0]alkane‐1‐carboxylates in yields ranging from 54 to 84 % (10 examples). The starting materials were obtained by sulfonylation of N‐alkenylanilines with methyl (chlorosulfonyl)acetate and subsequent bromination. For the N‐alkenylanilines (10 examples, 60–77 % yield) an efficient new synthesis employing a 2‐nitrophenylsulfonyl substituent as a protective as well as an activating group has been developed. The 4‐methoxyphenyl (PMP) group could easily be removed from the sultam nitrogen atom by treatment with cerium(IV) ammonium nitrate.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Geospatial analysis of controls on subglacial bedform morphometry in the New York Drumlin Field – implications for Laurentide Ice Sheet dynamics
Authors: Hess Dale P. , Briner Jason P.
Published: April 2009

The outline and trend of 6566 subglacial bedforms in the New York Drumlin Field have been digitized from digital elevation data. A spatial predictive model has been used to extend values of bedform elongation over an area measuring 200 km × 110 km. The resulting surface is used in conjunction with depth‐to‐bedrock data and an assumed duration of ice residence to test three proposed controls on bedform elongation. Upon comparison, the resulting display of morphometry is best explained by differences in ice velocity across the field of study. The existence of multiple zones of fast‐moving ice located along the southern margin of the Laurentide Ice Sheet is implied by the observed patterns of bedform elongation and orientation. We present two interpretations that are consistent with the observations. First, enhanced basal sliding caused by decreasing effective pressure near a calving margin is suggested as a possible mechanism by which localized fast ice flow is initiated and maintained. Second, topographically controlled ice streams likely occupied the fjord‐like troughs of the Appalachian Upland northern rim. Contrary to previous understanding of the Laurentide southern margin in New York State, the resulting palaeoglaciological reconstruction illustrates a dynamic mosaic of ice stream and/or outlet glacier activity. Copyright © 2009 John Wiley & Sons, Ltd.
Improving advance rates of TBMs in adverse ground conditions
Authors: Home Lok
Published: April 2009

A new approach is required to TBM tunneling where adverse ground conditions exist if predictable advance rates are to be achieved. It is well understood that when good ground conditions exist, TBMs vastly outperform drill and blast advance rates. However, with today's available TBMs, these high performance rates can soon be negated if adverse ground conditions are encountered. It is a common misconception that a shielded TBM will be able to cope with all adverse conditions. This is definitely not the case, as projects like Pinglin in Taiwan, Hallandsås in Sweden and San Francisco in Ecuador, will attest to.

This paper describes adverse ground conditions as related to TBM tunneling, including squeezing ground, rock bursts, fault zones, and high water pressure. Optimal ground support techniques and potential problems with specific TBM types are discussed. Finally, a new concept TBM that integrates both ground conditioning and ground control techniques is introduced. This new concept TBM endeavors to facilitate predictable advance rates, even in difficult conditions, using novel concepts such as a retractable front shield and improved rock support systems in L2 area. This retractable front shield incorporated into a Double Shield feature allows for immediate ground conditioning behind the cutter head and 360 degree probe drilling, while still maintaining the increased safety and simultaneous tunnel lining characteristic of Double Shield TBMs.

Excellent access immediately behind the cutter head is maintained by eliminating the peripheral thrust cylinder utilized in standard shields and using the basic floating gripper design to pass thrust to the cutter head via a main beam.
Simple and practical TBM performance prediction
Authors: Tarkoy Peter J.
Published: April 2009

The prediction of excavation rates for tunnel boring was originally developed for rock boring machines. One of the earliest working methods for predicting TBM performance was developed at the University of Illinois. The method was simple, reliable, inexpensive, and the data available to the public. Since then, various methods, more sophisticated, more time consuming and more expensive have been developed by various researchers. Some of them were quite exacting in the prediction despite a limited knowledge of anticipated conditions. Others were ever changing and unavailable for public use.

Predictions of penetration rates and disc cutter consumption were tied to rock properties and machine variables while the prediction of TBM utilization was ignored even though in many cases it was the most variable element having the greatest impact. Prediction of TBM utilization was substantially more difficult since it was a function of time and length dependent downtimes, project conditions, TBM design features, work force, construction management, and site limitations. Many of these influences were simply a function of the impact of the human element and therefore tenuous to predict.

The development of machines designed to negotiate soil, rock, and a combination of both inherently imposed additional influences on the productivity. An increase in the use of electronic technology in tunnel boring, both for control functions and recording of instantaneous machine variables have allowed the imposition of additional constraints, such as thrust & torque limitations.

How do we take all of these additional variables into account in the forecasting of TBM performance?