bluuebunny/crossref_metadata_2025 huggingface dataset:
Identifying Forces Driving PMO Changes
Authors: Aubry Monique , Hobbs Brian , Müller Ralf , Blomquist Tomas
Published: June 2010

Project management offices (PMOs) are dynamic organizational entities, frequently in transition from one charter and structure to the next. Within this article, we present empirical results on the nature and reasons for this transition. The article reports the second of a series of studies aimed at understanding the dynamics of PMOs. It addresses the mistaken paradigm that PMOs change because characteristics or functions in an existing PMO are wrong and require a new PMO charter or structure that can last for a long time. Instead of that, the article proposes a process view on the transformation of the PMO as being triggered by conditions within the external and/or internal context and producing outcomes in terms of impacts from the transformation. A global web-based questionnaire on PMO transitions in structure and charter yielded 184 responses. Factor analysis and correlation analyses revealed that the transition of a PMO from one configuration to the next is not a question of being right or wrong. PMOs in transition can rather be understood as a multilevel dynamic process anchored in a specific organizational context change. From the academic viewpoint, the authors believe that this research filled a large gap in the under-standing of the reasons for and nature of PMOs to transition.
Current treatment options in the management of psoriasis
Authors: Higgins Eleanor , Markham Trevor
Published: June 2010

Psoriasis is a common chronic condition and treatment choice primarily centres on disease severity. Our Drug review considers the therapeutic options, their properties and safety profiles, followed by sources of further information and an analysis of prescription data. Copyright © 2010 Wiley Interface Ltd
Comparison of ginsenosides Rg1 and Rb1 for their effects on improving scopolamine‐induced learning and memory impairment in mice
Authors: Wang Qiong , Sun Li‐Hua , Jia William , Liu Xin‐Min , Dang Hai‐Xia , Mai Wen‐Li , Wang Ning , Steinmetz Andre , Wang Yu‐Qin , Xu Chang‐Jiang
Published: June 2010

Rg1 and Rb1 are two major active compounds of ginseng that facilitate learning and memory. The present study aimed to compare the nootropic effects of Rg1 and Rb1 in a scopolamine induced dementia mice model. After 6 and 12 mg/kg of Rg1 and Rb1 intraperitoneal administration to mice for 7 days, their effects were assessed using the step‐down passive avoidance (SD) and the Morris water maze (MWM) tests, the acetylcholinesterase (AChE) activity, acetylcholine (ACh) content and serotonin (5‐HT) level in the hippocampus were analysed after SD and MWM tests. The results showed that Rg1 and Rb1 ameliorated cognition‐deficiency in mice with dementia. Rg1 showed stronger effects than Rb1 on escape acquisition in MWM. Both Rg1 and Rb1 increased ACh levels in the hippocampus, but Rg1 inhibited AChE activity while Rb1 had no effect on AChE activity. Both Rg1 and Rb1 inhibited the decrease of 5‐HT induced by scopolamine, but Rb1 was more active than the same dose of Rg1. These results demonstrate that multiple administrations of Rg1 and Rb1 are effective in improving memory deficiency induced by scopolamine. Rg1 appears to be more potent than Rb1 in improving acquisition impairment, and the two ginsenosides may act through different mechanisms. Copyright © 2010 John Wiley & Sons, Ltd.
Antiinflammatory effects of Epimedium brevicornum water extract on lipopolysaccharide‐activated RAW264.7 macrophages
Authors: Yuk Sang‐Suk , Lim Eun‐Mee , Lee Ji Young , Lee Young‐Jong , Kim Yoon‐Sang , Lee Tae Hee , Park Seong Kyu , Bae Hyunsu , Kim Hyung Min , Ko Seong‐Gyu , Oh Myung Sook , Park Wansu
Published: June 2010

Epimedium brevicornum Maxim (Berberidaceae) possesses estrogenic properties. It is one of the most widespread herbal remedies used in Oriental medicine. The present study investigated the effects of Epimedium brevicornum water extract (EB) on proinflammatory mediators secreted from lipopolysaccharide (LPS)‐induced RAW264.7 macrophages. EB significantly inhibited the production of nitric oxide (NO), interleukin (IL)‐3, IL‐10, IL‐12p40, interferon‐inducible protein‐10, keratinocyte‐derived chemokine, vascular endothelial growth factor, monocyte chemotactic protein‐1 and granulocyte macrophage‐colony stimulating factor in LPS‐induced RAW264.7 cells at concentrations of 25, 50, 100 and 200 μg/mL (p < 0.05). These results suggest that EB has antiinflammatory activity related to its inhibition of NO, cytokine, chemokine and growth factor production in macrophages. Copyright © 2010 John Wiley & Sons, Ltd.
In vitro screening of tumoricidal properties of international medicinal herbs: part II
Authors: Mazzio Elizabeth A. , Soliman Karam F. A.
Published: June 2010

With growing use of anticancer complementary and alternative medicines (CAMs) worldwide, there is a need to assess and screen commercially available natural products for relative tumoricidal properties under standard experimental conditions. In the current study, we screened and ranked 264 traditional Chinese and Egyptian herbal medicines for tumoricidal potency against malignant neuroblastoma in vitro. The data obtained show that tumoricidal potencies of plants were randomly dispersed throughout similar orders, families and genera under the Division: Magnoliophyta, class: Magnoliopsida, subclasses: Asteridae, Caryophyllidae, Dilleniidae, Hamamelididae, Magnoliidae and Rosidae. The most potent plant extracts (LC50 < 0.08 mg/ml) were prepared from gromwell root also known as ‘Hong Tiao Zi Cao’ (Lithospermum Erythrorhizon) Family (Boraginaceae) > beth root (Trillium Pendulum), Family (Liliaceae) and galbanum (Ferula Galbaniflua), Family (Apiaceae). Gromwell root is traditionally used in the preparation of Chinese medicinal tea. In addition, galbanum was highly regarded for its sacred and medicinal value according to ancient texts and the bible. Future research will be required to isolate and identify chemical constituents within these plants which are responsible for tumoricidal effects. Copyright © 2010 John Wiley & Sons, Ltd.
Grape seed extract prevents azathioprine toxicity in rats
Authors: El‐Ashmawy Ibrahim M. , Gad Shereen B. , Salama Osama M.
Published: June 2010

Azathioprine (Aza) is an important drug commonly used in the therapy of autoimmune system disorders. It induces hepatotoxicity and hazard effects that restrict its use. The effects of administration of grape seed extract and folic acid on Aza toxicity by gavage (simultaneously) daily for 4 weeks were studied by determining the changes in some hematological parameters and liver histology. The glutathione level (GSH) and lipid peroxidation content as malondialdehyde (MDA) in the liver tissue were measured. The repeated intake of Aza (25 mg/kg body weight) induced anemia characterized by decreased erythrocyte and leukocyte counts and reticulocyte and hematocrit percentages, while the prothrombin time was significantly increased. Moreover, Aza caused a significant decrease in phagocytic activity and lymphocyte percentage. Aza induced hepatic damage as indicated by pronounced changes in the histological structure, a significant increase in serum aspartate aminotransferase (AST), alanine aminotransferase (ALT) and alkaline phosphatase (ALP), and MDA content in the liver tissue. Meanwhile, the GSH activity was significantly decreased. Co‐treatment with grape seed extract and Aza minimized the previously mentioned hazard effects of Aza and significantly protected the hepatic tissue by ameliorating the antioxidant activity. Folic acid administration, simultaneously, with Aza only improved the anemia. It may be concluded that grape seed extract is a useful herbal remedy, especially for controlling oxidative damages and is considered as a potent protective agent against Aza hepatotoxicity. Copyright © 2010 John Wiley & Sons, Ltd.
Zingiber officinale (ginger) compounds have tetracycline‐resistance modifying effects against clinical extensively drug‐resistant Acinetobacter baumannii
Authors: Wang Hui‐Min , Chen Chung‐Yi , Chen Hsi‐An , Huang Wan‐Chun , Lin Wei‐Ru , Chen Tun‐Chieh , Lin Chun‐Yu , Chien Hsin‐Ju , Lu Po‐Liang , Lin Chiu‐Mei , Chen Yen‐Hsu
Published: June 2010

Extensively drug‐resistant Acinetobacter baumannii (XDRAB) is a growing and serious nosocomial infection worldwide, such that developing new agents against it is critical. The antimicrobial activities of the rhizomes from Zingiber officinale, known as ginger, have not been proven in clinical bacterial isolates with extensive drug‐resistance. This study aimed to investigate the effects of four known components of ginger, [6]‐dehydrogingerdione, [10]‐gingerol, [6]‐shogaol and [6]‐gingerol, against clinical XDRAB. All these compounds showed antibacterial effects against XDRAB. Combined with tetracycline, they showed good resistance modifying effects to modulate tetracycline resistance. Using the 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radical scavenging method, these four ginger compounds demonstrated antioxidant properties, which were inhibited by MnO2, an oxidant without antibacterial effects. After the antioxidant property was blocked, their antimicrobial effects were abolished significantly. These results indicate that ginger compounds have antioxidant effects that partially contribute to their antimicrobial activity and are candidates for use in the treatment of infections with XDRAB. Copyright © 2010 John Wiley & Sons, Ltd.
Protein tyrosine phosphatase 1B inhibitory activity of 24‐norursane triterpenes isolated from Weigela subsessilis
Authors: Na MinKyun , Thuong Phuong Thien , Hwang In Hyun , Bae KiHwan , Kim Bo Yeon , Osada Hiroyuki , Ahn Jong Seog
Published: June 2010

During the screening effort to discover new types of protein tyrosine phosphatase 1B (PTP1B) inhibitors, it was found that a MeOH extract of the leaves and stems of Weigela subsessilis (Caprifoliaceae) inhibited the enzyme activity. By means of an in vitro bioassay‐guided fractionation on the MeOH extract, two 24‐norursane triterpenes, ilekudinol A (1) and ilekudinol B (2), were isolated as active metabolites. Compounds 1 and 2 inhibited PTP1B with IC50 values of 29.1 ± 2.8 and 5.3 ± 0.5 μM, respectively. Kinetic studies suggest that both 1 and 2 are non‐competitive inhibitors of PTP1B. The findings indicate that the free carboxyl group at C‐28 in this type of triterpenes plays a critical role in the inhibition of PTP1B. Copyright © 2010 John Wiley & Sons, Ltd.
Antiarrhythmic effects and ionic mechanisms of oxymatrine from Sophora flavescens
Authors: Yong‐gang Cao , Shan Jing , Lei Li , Jing‐quan Gao , Zhi‐ying Shen , Yan Liu , Yan Xing , Ming‐li Wu , Ye Wang , Chang‐qing Xu , Hong‐li Sun
Published: June 2010

Accumulating evidence indicates that oxymatrine may exert protective effects on the cardiovascular system. This study was designed to evaluate the antiarrhythmic effects as well as the electrophysiological properties of oxymatrine. The antiarrhythmic activity of oxymatrine was observed in a rat model of arrhythmia induced by coronary ligation. Action potential duration (APD), L‐type calcium current (ICa‐L), transient outward potassium current (Ito) and inward rectifier potassium current (IK1) in rat ventricular myocytes were recorded by utilizing the whole cell patch‐clamp technique. The results showed that administration of oxymatrine significantly delayed the onset of ventricular arrhythmia, decreased the duration of ventricular arrhythmia and reduced the arrhythmia score of arrhythmic rats. The beneficial effects of oxymatrine may be related to the shortening of APD through reduction of ICa‐L, enhancement of Ito and inhibition of IK1. Copyright © 2010 John Wiley & Sons, Ltd.
Antimycobacterial, antiprotozoal and cytotoxic potential of twenty‐one brown algae (phaeophyceae) from British and Irish waters
Authors: Spavieri Jasmine , Allmendinger Andrea , Kaiser Marcel , Casey Rosalyn , Hingley‐Wilson Suzie , Lalvani Ajit , Guiry Michael D. , Blunden Gerald , Tasdemir Deniz
Published: June 2010

In the continuation of our research on seaweeds, crude extracts of 21 brown algae collected from the south coast of England and the west coast of Ireland were screened for in vitro trypanocidal, leishmanicidal and antimycobacterial activities. Mammalian stages of a small set of parasitic protozoa; i.e. Trypanosoma brucei rhodesiense, T. cruzi and Leishmania donovani, and the tubercle bacillus Mycobacterium tuberculosis were used as test organisms. The extracts were also evaluated for selectivity by testing on a mammalian cell line (L6 cells). Only four extracts were moderately active against T. cruzi, whereas all algal extracts showed significant activity against T. brucei rhodesiense, with Halidrys siliquosa and Bifurcaria bifurcata (Sargassaceae) being the most potent (IC50 values 1.2 and 1.9 μg/mL). All algal extracts also displayed leishmanicidal activity, with H. siliquosa and B. bifurcata again being the most active (IC50s 6.4 and 8.6 μg/mL). When tested against M. tuberculosis, only the B. bifurcata extract was found to have some antitubercular potential (MIC value 64.0 μg/mL). Only three seaweed extracts, i.e. H. siliquosa, B. bifurcata and Cystoseira tamariscifolia showed some cytotoxicity. To our knowledge, this is the first study on the antiprotozoal and antimycobacterial activity of brown algae from British and Irish waters. Copyright © 2010 John Wiley & Sons, Ltd.
Activation of AMP‐activated protein kinase on human gastric cancer cells by apoptosis induced by corosolic acid isolated from Weigela subsessilis
Authors: Lee Myung Sun , Lee Chang Min , Cha Eun Young , Thuong Phuong Thien , Bae KiHwan , Song In Sang , Noh Seung Moo , Sul Ji Young
Published: June 2010

Corosolic acid is one of the triterpenoids present in the leaves of Weigela subsessilis. The antidiabetic activity of corosolic acid has been reported previously, but to date, the anticancer effects on gastric cancer have been poorly studied. In this study, corosolic acid showed growth inhibition on SNU‐601 human gastric cancer cells, with an IC50 value of 16.9 ± 2.9 μm. Corosolic acid also triggered the activation of caspase‐3 and poly (ADP‐ribose) polymerase, while it was recovered by Z‐VAD‐FMK. Moreover, the cell growth/apoptosis activities of corosolic acid were regulated by the AMP‐activated protein kinase‐mammalian target of rapamycin (AMPK‐mTOR) signals. These results showed that corosolic acid‐mediated AMPK activation leads to inhibition of mTOR, thus providing a possible mechanism of action of corosolic acid in the inhibition of cancer cell growth and the induction of apoptosis. Copyright © 2010 John Wiley & Sons, Ltd.
Effect of an antidiabetic polysaccharide from Inula japonica on constipation in normal and two models of experimental constipated mice
Authors: Shan J. J. , Zhang Y. , Diao Y. L. , Qu W. S. , Zhao X. N.
Published: June 2010

OBJECTIVES: The aim of the present study was to investigate the effect of an antidiabetic polysaccharide (IJP) from Inula japonica on gastrointestinal transit in normal mice and on constipation in two models of constipated mice.

METHODS: Two models of constipation in mice were respectively induced by fasted water for 4 days or induced by diphenoxylate. The normal and constipated mice were administered IJP once at doses of 100 and 400 mg/kg (p.o.), the gastrointestinal vermicular motion, start time of defecation, number and weight of stool were investigated.

RESULTS: After administration of IJP, the gastrointestinal propulsive rate was increased by 9.79% and 10.42%, the start time of defecation was shortened by 37.27% and 44.06%, the number of feces increased by 115.4% and 130.8% in normal mice. In fasting‐water constipated mice, the start time of defecation was shortened by 9.69% and 30.52% by IJP, defecation granules raised by 22.09% and 39.53%, wet feces weights were increased by 23.50% and 39.14% compared with the untreated constipated mice. In diphenoxylate‐induced mice, the start time of defecation was shortened by 25.48% and 28.13%, defecation granules raised by 100.0% and 118.0%.

CONCLUSIONS: Consumption of IJP effectively improved bowel movement, stool output observed in this study. IJP may be practical in relieving constipation in the elderly diabetic population. Copyright © 2010 John Wiley & Sons, Ltd.
Blueberry anthocyanins and pyruvic acid adducts: anticancer properties in breast cancer cell lines
Authors: Faria Ana , Pestana Diogo , Teixeira Diana , de Freitas Victor , Mateus Nuno , Calhau Conceição
Published: June 2010

The purpose of this study was to investigate the anticancer properties of an anthocyanin‐pyruvic acid adduct extract, which is being developed aiming to be further applied in the food industry. An anthocyanin extract from blueberry (extract I) and an anthocyanin‐pyruvic acid adduct extract (extract II) were tested on two breast cancer cell lines (MDA‐MB‐231 and MCF7). Proliferation was assessed by SRB assay and 3H‐thymidine incorporation. Caspase‐3 activity was determined in the presence of both extracts. Their capacity as chemoattractants and their invasive potential were also assayed.

In both cell lines, extracts I and II significantly reduced cell proliferation at 250 μg/mL, after 24 h of cell incubation. Caspase‐3 activity was not altered by the extracts (250 μg/mL) in either cell line, with the exception of extract II in MCF‐7, which increased its activity, probably explaining its effects on cell proliferation.

Both extracts (250 μg/mL) demonstrated significant antiinvasive potential in both cell lines. Furthermore, they did not demonstrate any capacity for chemotaxis.

In conclusion, blueberry anthocyanins and the respective anthocyanin‐pyruvic acid adducts demonstrated anticancer properties by inhibiting cancer cell proliferation and by acting as cell antiinvasive factors and chemoinhibitors. The anthocyanin‐pyruvic acid adduct extract showed a more pronounced effect in MDA‐MB‐231, suggesting an effect independent of estrogen receptors. Copyright © 2010 John Wiley & Sons, Ltd.
Cycloartane triterpenoids from Cimicifuga yunnanensis induce apoptosis of breast cancer cells (MCF7) via p53‐dependent mitochondrial signaling pathway
Authors: Fang Zhong‐Ze , Nian Yin , Li Wei , Wu Jing‐Jing , Ge Guang‐Bo , Dong Pei‐Pei , Zhang Yan‐Yan , Qiu Ming‐Hua , Liu Lei , Yang Ling
Published: June 2010

The present study was carried out to investigate the antitumor activity of five cycloartane triterpenoids isolated from Cimicifuga yunnanensis on the breast cancer cell line MCF7 and its corresponding drug resistant subline R‐MCF7, including cimigenol‐3‐O‐β‐d‐xylopyranoside (compound 1), 25‐O‐acetylcimigenol‐3‐O‐β‐d‐xylopyranoside (compound 2), 25‐chlorodeoxycimigenol‐3‐O‐β‐d‐xylopyranoside (compound 3), 25‐O‐acetylcimigenol‐3‐O‐α‐l‐arabinopyranoside (compound 4) and 23‐O‐acetylcimigenol‐3‐O‐β‐d‐xylopyranoside (compound 5). The results showed that compounds 2–5 have relatively high antitumor activity on both MCF7 and R‐MCF7 cells. The involvement of apoptosis as a major cause of cycloartane triterpenoids‐induced cell death was further confirmed. The results of RT‐PCR showed that compounds 2–5 increased the expression of p53 and bax, which led to the loss of mitochondrial potential and then resulted in the activation of caspase‐7. These findings collectively demonstrated that compounds 2–5 induced apoptosis of MCF7 via p53‐dependent mitochondrial pathway. Copyright © 2010 John Wiley & Sons, Ltd.
Methylation of acidic moieties in poly(methyl methacrylate‐co‐methacrylic acid) copolymers for end‐group characterization by tandem mass spectrometry
Authors: Giordanengo Rémi , Viel Stéphane , Hidalgo Manuel , Allard‐Breton Béatrice , Thévand André , Charles Laurence
Published: June 2010

The complete structural characterization of a copolymer composed of methacrylic acid (MAA) and methyl methacrylate (MMA) units was achieved using tandem mass spectrometry. In a first step, collision‐induced dissociation (CID) of sodiated MAA‐MMA co‐oligomers allowed us to determine the co‐monomeric composition, the random nature of the copolymer and the sum of the end‐group masses. However, dissociation reactions of MAA‐based molecules mainly involve the acidic pendant groups, precluding individual characterization of the end groups. Therefore, methylation of all the acrylic acid moieties was performed to transform the MAA‐MMA copolymer into a PMMA homopolymer, for which CID mainly proceeds via backbone cleavages. Using trimethylsilyldiazomethane as a derivatization agent, this methylation reaction was shown to be complete without affecting the end groups. Using fragmentation rules established for PMMA polymers together with accurate mass measurements of the product ions and knowledge of reagents used for the studied copolymer synthesis, a structure could be proposed for both end groups and it was found to be consistent with signals obtained in nuclear magnetic resonance spectra. Copyright © 2010 John Wiley & Sons, Ltd.
Quadrupole mass filters with added hexapole fields
Authors: Xiao Zilan , Zhao XianZhen , Douglas D. J.
Published: June 2010

Conventional mass analysis has been investigated experimentally with six quadrupole mass filters with added hexapole fields; three with added hexapole fields of 4%, 8% and 12% with equal diameter rods, and three with added hexapole fields of 4%, 8% and 12% with unequal diameter rods to remove an added octopole field. Compared with conventional quadrupoles, these rod sets have very large field distortions. With the positive resolving dc applied to the y rods (Mathieu parameter $a_{x} < 0$) only low resolution (10–100) and low transmission are seen. With the polarity reversed ($a_{x} > 0$) much higher resolution (≥1000) and transmission are possible. Increasing the magnitude of the added hexapole field decreases the limiting resolution at m/z 609. Removing the added octopole field increases the limiting resolution. In some cases structure is formed on the peaks. For a given scan line slope, U/V

rf
, the resolution decreases as the amplitude of the added hexapole field increases. These results are consistent with changes to the stability diagrams, calculated here. With $a_{x} > 0$, adding a hexapole field causes the x stability boundary to move outward with all rod sets. With $a_{x} < 0$, the boundaries become diffuse and the tip of the stability diagram becomes rounded, limiting the resolution to ca. 10‐100. Where comparisons are possible, experiments show the rod sets with added hexapole fields have transmission 10–300 times less than a conventional quadrupole. Thus these quadrupoles are less useful for mass analysis than conventional quadrupoles. However, it is surprising, given the highly distorted fields, that some of the quadrupoles give resolution of 1000 or more. Copyright © 2010 John Wiley & Sons, Ltd.
Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes
Authors: Santamaria‐Fernandez Rebeca , Wolff Jean‐Claude
Published: June 2010

The potential of high‐precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA‐MC‐ICP‐MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA‐MC‐ICP‐MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in‐house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured‐corrected Ca isotope ratio values (43Ca/44Ca and 42Ca/44Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured‐corrected Pb isotope ratios (207Pb/206Pb and 208Pb/206Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)‐ICP‐MS instrument. The use of LA‐MC‐ICP‐MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. Copyright © 2010 John Wiley & Sons, Ltd.
Error assessment of nitrogen and oxygen isotope ratios of nitrate as determined via the bacterial denitrification method
Authors: Xue Dongmei , De Baets Bernard , Vermeulen Jan , Botte Jorin , Van Cleemput Oswald , Boeckx Pascal
Published: June 2010

Currently, bacterial denitrification is becoming the accepted method for δ15N‐ and δ18O‐NO determination. However, proper correction methods with international references (USGS32, USGS34 and USGS35) are needed. As a consequence, it is important to realize that the corrected isotope values are derived from a combination of several other measurements with associated uncertainties. Therefore, it is necessary to consider the propagated uncertainty on the final isotope value. This study demonstrates how to correctly estimate the uncertainty on corrected δ15N‐ and δ18O‐NO values using a first‐order Taylor series approximation. The bacterial denitrification method errors from 33 batches of 561 surface water samples varied from 0.2 to 2.1‰ for δ15N‐NO and from 0.7 to 2.3‰ for δ18O‐NO, which is slightly wider than the machine error, which varied from 0.2 to 0.6‰ for δ15N‐N2O and from 0.4 to 1.0‰ for δ18O‐N2O. The overall uncertainties, which are composed of the machine error and the method error, for the 33 batches ranged from 0.3 to 2.2‰ for δ15N‐NO and from 0.8 to 2.5‰ for δ18O‐NO. In addition, the mean corrected δ15N and δ18O values of 132 KNO3‐IWS (internal working standard) measurements were computed as 8.4 ± 1.0‰ and 25.1 ± 2.0‰, which is a slight underestimation for δ15N and overestimation for δ18O compared with the accepted values (δ15N = 9.9 ± 0.3‰ and δ18O = 24.0 ± 0.3‰). The overall uncertainty of the bacterial denitrification method allows the use of this method for source identification of NO. Copyright © 2010 John Wiley & Sons, Ltd.
Identification of complex, naturally occurring flavonoid glycosides in kale (Brassica oleracea var. sabellica) by high‐performance liquid chromatography diode‐array detection/electrospray ionization multi‐stage mass spectrometry
Authors: Schmidt Susanne , Zietz Michaela , Schreiner Monika , Rohn Sascha , Kroh Lothar W. , Krumbein Angelika
Published: June 2010

Kale is a member of the Brassicaceae family and has a complex profile of flavonoid glycosides. Therefore, kale is a suitable matrix to discuss in a comprehensive study the different fragmentation patterns of flavonoid glycosides. The wide variety of glycosylation and acylation patterns determines the health‐promoting effects of these glycosides. The aim of this study is to investigate the naturally occurring flavonoids in kale. A total of 71 flavonoid glycosides of quercetin, kaempferol and isorhamnetin were identified using a high‐performance liquid chromatography diode‐array detection/electrospray ionization multi‐stage mass spectrometry (HPLC‐DAD/ESI‐MSn) method. Of these 71 flavonol glycosides, 27 were non‐acylated, 30 were monoacylated and 14 were diacylated. Non‐acylated flavonol glycosides were present as mono‐, di‐, tri‐ and tetraglycosides. This is the first time that the occurrence of four different fragmentation patterns of non‐acylated flavonol triglycosides has been reported in one matrix simultaneously. In addition, 44 flavonol glycosides were acylated with p‐coumaric, caffeic, ferulic, hydroxyferulic or sinapic acid. While monoacylated glycosides existed as di‐, tri‐ and tetraglycosides, diacylated glycosides occurred as tetra‐ and pentaglycosides. To the best of our knowledge, 28 compounds in kale are reported here for the first time. These include three acylated isorhamnetin glycosides (isorhamnetin‐3‐O‐sinapoyl‐sophoroside‐7‐O‐D‐glucoside, isorhamnetin‐3‐O‐feruloyl‐sophoroside‐7‐O‐diglucoside and isorhamnetin‐3‐O‐disinapoyl‐triglucoside‐7‐O‐diglucoside) and seven non‐acylated isorhamnetin glycosides. Copyright © 2010 John Wiley & Sons, Ltd.
Software tool for mining liquid chromatography/multi‐stage mass spectrometry data for comprehensive glycerophospholipid profiling
Authors: Hein Eva‐Maria , Bödeker Bertram , Nolte Jürgen , Hayen Heiko
Published: June 2010

Electrospray ionization mass spectrometry (ESI‐MS) has emerged as an indispensable tool in the field of lipidomics. Despite the growing interest in lipid analysis, there are only a few software tools available for data evaluation, as compared for example to proteomics applications. This makes comprehensive lipid analysis a complex challenge. Thus, a computational tool for harnessing the raw data from liquid chromatography/mass spectrometry (LC/MS) experiments was developed in this study and is available from the authors on request. The Profiler‐Merger‐Viewer tool is a software package for automatic processing of raw‐data from data‐dependent experiments, measured by high‐performance liquid chromatography hyphenated to electrospray ionization hybrid linear ion trap Fourier transform mass spectrometry (FTICR‐MS and Orbitrap) in single and multi‐stage mode. The software contains three parts: processing of the raw data by Profiler for lipid identification, summarizing of replicate measurements by Merger and visualization of all relevant data (chromatograms as well as mass spectra) for validation of the results by Viewer. The tool is easily accessible, since it is implemented in Java and uses Microsoft Excel (XLS) as output format. The motivation was to develop a tool which supports and accelerates the manual data evaluation (identification and relative quantification) significantly but does not make a complete data analysis within a black‐box system. The software's mode of operation, usage and options will be demonstrated on the basis of a lipid extract of baker's yeast (S. cerevisiae). In this study, we focused on three important representatives of lipids: glycerophospholipids, lyso‐glycerophospholipids and free fatty acids. Copyright © 2010 John Wiley & Sons, Ltd.
Post‐interface signal suppression, a phenomenon observed in a single‐stage Orbitrap mass spectrometer coupled to an electrospray interfaced liquid chromatograph
Authors: Kaufmann A. , Widmer M. , Maden K.
Published: June 2010

Signal suppression is a common issue when analyzing compounds by liquid chromatography coupled to mass spectrometry (LC/MS/MS). Suppression of signals is caused by co‐eluting matrix compounds and is thought to take place in the interface. This paper reports strong signal suppression effects which were observed when using a single‐stage Orbitrap instrument which was coupled by an electrospray interface to a liquid chromatograph. This type of signal suppression (often the complete loss of certain analyte signal) is observed in addition to signal suppression originating in the electrospray interface. The location of where this phenomenon occurs was shown to be clearly beyond the interface region. It was suspected that not the Orbitrap cell itself, but the C‐trap, which is an integral part within the Orbitrap instrument, was the probable location. Such post‐interface signal suppression was observed – and could be experimentally induced – when multiply charged ions (e.g. electrospray protonated proteins) were co‐eluting with the analytes. High concentrations of proteins, yet not exceeding the maximum ion capacity of the trap, can cause a complete loss of all low m/z masses. This paper describes the practical implication when analyzing heavy matrix samples and discusses strategies to reduce such detrimental effects. Copyright © 2010 John Wiley & Sons, Ltd.
Proton transfer reaction time‐of‐flight mass spectrometry monitoring of the evolution of volatile compounds during lactic acid fermentation of milk
Authors: Soukoulis Christos , Aprea Eugenio , Biasioli Franco , Cappellin Luca , Schuhfried Erna , Märk Tilmann D. , Gasperi Flavia
Published: June 2010

We apply, for first time, the recently developed proton transfer reaction time‐of‐flight mass spectrometry (PTR‐TOF‐MS) apparatus as a rapid method for the monitoring of lactic acid fermentation (LAF) of milk. PTR‐TOF‐MS has been proposed as a very fast, highly sensitive and versatile technique but there have been no reports of its application to dynamic biochemical processes with relevance to the food industry.

LAF is a biochemical‐physicochemical dynamic process particularly relevant for the dairy industry as it is an important step in the production of many dairy products. Further, LAF is important in the utilization of the by‐products of the cheese industry, such as whey wastewaters.

We show that PTR‐TOF‐MS is a powerful method for the monitoring of major volatile organic chemicals (VOCs) formed or depleted during LAF, including acetaldehyde, diacetyl, acetoin and 2‐propanone, and it also provides information about the evolution of minor VOCs such as acetic acid, 2,3‐pentanedione, ethanol, and off‐flavor related VOCs such as dimethyl sulfide and furfural. This can be very important considering that the conventional measurement of pH decrease during LAF is often ineffective due to the reduced response of pH electrodes resulting from the formation of protein sediments. Solid‐phase microextraction gas chromatography/mass spectrometry (SPME‐GC/MS) data on the inoculated milk base and final fermented product are also presented to supporting peak identification. We demonstrate that PTR‐TOF‐MS can be used as a rapid, efficient and non‐invasive method for the monitoring of LAF from headspace, supplying important data about the quality of the final product and that it may be used to monitor the efficacy of manufacturing practices. Copyright © 2010 John Wiley & Sons, Ltd.
Direct profiling of phospholipids and lysophospholipids in rat brain sections after ischemic stroke
Authors: Wang Hay‐Yan J. , Liu Cheng Bin , Wu Hsuan‐Wen , Kuo Jr Shin
Published: June 2010

Stroke, a deleterious cerebrovascular event, is caused by a critical reduction in the blood flow to the brain parenchyma that leads to brain injury and loss of brain functions. The inflammatory responses following ischemia often aggravate the neurological damage. Several pro‐inflammatory mediators released after stroke are closely related to the metabolism of phospholipids. In this study we directly profiled the changes in phospholipids in the infarcted rat cerebral cortex 24 hours after middle cerebral artery occlusion (MCAO) using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). Several phosphatidylcholine (PC) species and sphingomyelin (SM) were significantly decreased after infarction. The cationization pattern of the remaining PCs showed a prominent shift from a mostly potassiated or protonated form to a predominantly sodiated pattern. Stroke also elevated the lysophosphatidylcholines (LPCs) and heme in tissue. The isobaric pairs in PC and LPC classes were resolved by masses through their respective alkali metal adducts in the presence of CsCl. The major fatty acyl LPC species were also structurally confirmed by MALDI‐MS/MS. Overall, the results described the changes in PC and LPC species in the infarcted rat cortex. The elevated tissue levels of LPCs and heme signify the ongoing pathological lipid breakdown and the state of parenchymal inflammation. The elevated LPC level in tissue suggests a means of intervention through lysophospholipid metabolism that could potentially benefit the management of stroke and other acute neurological injuries. Copyright © 2010 John Wiley & Sons, Ltd.
Fragmentation studies and electrospray ionization mass spectrometry of lapachol: protonated, deprotonated and cationized species
Authors: Vessecchi Ricardo , Emery Flavio S. , Galembeck Sérgio E. , Lopes Norberto P.
Published: June 2010

Electrospray ionization mass spectrometric analysis of lapachol (2‐hydroxy‐3‐(3‐methyl‐2‐butenyl)‐1,4‐naphthoquinone) was accomplished in order to elucidate the gas‐phase dissociation reactions of this important biologically active natural product. The occurrence of protonated and cationized species in the positive mode and of deprotonated species in the negative mode was explored by means of collision‐induced dissociation (CID) experiments. For the protonated molecule, the H2O and C4H8 losses occur by two competitive channels. For the deprotonated molecule, the even‐electron rule is not conserved, and the radicalar species are eliminated by formation of distonic anions. The fragmentation mechanism for each ion was suggested on the basis of computational thermochemistry. Atomic charges, relative energies, and frontier orbitals were employed aiming at a better understanding of the gas‐phase reactivity of lapachol. Potential energy surfaces for fragmentation reactions were obtained by the B3LYP/6‐31+G(d,p) model. Copyright © 2010 John Wiley & Sons, Ltd.
Influence of substituent groups at the 3‐position on the mass spectral fragmentation pathways of cephalosporins
Authors: Li Jin , Zhang Dou‐sheng , Chong Xiao‐meng , Hu Chang‐qin
Published: June 2010

The structural fragment ions of nine cephalosporins were studied by electrospray ionization quadrapole trap mass spectrometry (Q‐Trap MSn) in positive mode. The influence of substituent groups in the 3‐position on fragmentation pathway B, an α‐cleavage between the C7C8 single bond, coupled with a [2,4]‐trans‐Diels‐Alder cleavage simultaneously within the six‐membered heterocyclic ring, was also investigated. It was found that when the substituent groups were methyl, chloride, vinyl, or propenyl, fragmentations belonging to pathway B were detected; however, when the substituents were heteroatoms such as O, N, or S, pathway B fragmentation was not detected. This suggested that the [M–R3]+ ion, which was produced by the bond cleavage within the substituent group at the 3‐position, had a key influence on fragmentation pathway B. This could be attributed to the strong electronegativity of the heteroatoms (O, N, S) that favors the production of the [M–R3]+ ion. Moreover, having the positive charge of the [M–R3]+ ion localized on the nitrogen atom in the 1‐position changed the electron density distribution of the heterocyclic structure, which prohibits a [2,4]‐reverse‐Diels‐Alder fragmentation and as a result fragmentation pathway B could not occur. The influence of the substituent group in the 3‐position was determined by the intensity ratio (e/d) of ions produced by fragmentation pathway A, a [2,2]‐trans‐Diels‐Alder cleavage within the quaternary lactam ring, including the breaking of the amide bond and the C6C7 single bond (ion d), and fragmentation pathway B (ion e). The results indicate that the electronegativity of the substituent group was a key influencing factor of pathway B fragmentation intensity, because the intensity ratio (e/d) is higher for a chlorine atom, a vinyl, or a propenyl group than that of a methyl group. This study provided some theoretical basis for the identification of cephalosporin antibiotics and structural analysis of related substances in drugs. Copyright © 2010 John Wiley & Sons, Ltd.
Compound‐specific bromine isotope analysis of brominated diphenyl ethers using gas chromatography multiple collector/inductively coupled plasma mass spectrometry
Authors: Holmstrand Henry , Unger Maria , Carrizo Daniel , Andersson Per , Gustafsson Örjan
Published: June 2010

The bromine isotope composition is potentially diagnostic in both degradation monitoring and source apportionment of organobromines in the environment. A method for compound‐specific bromine isotope analysis (δ81Br) based on gas chromatography multiple collector inductively coupled plasma mass spectrometry (GC/ICPMS) was developed for common brominated diaromatic compounds. Brominated diphenyl ethers (BDEs) in Bromkal 70‐5DE, a technical flame‐retardant mixture containing mainly BDEs #47, #99 and #100, were used as test substances, with standard bracketing for the samples achieved through co‐injected monobromobenzene (MBB) with a known δ81Br of −0.39‰ vs. Standard Mean Ocean Bromine (SMOBr). Three different heated transfer lines were constructed and tested to achieve efficient conduction of the BDEs from the gas chromatograph to the ICPMS instrument. The MBB was analyzed with a precision of 0.4‰ (1 s, n = 18). The precision for BDEs was 1.4–1.8‰ (1 s, n = 10–12 depending on the congener). The lower precision for the BDEs than for MBB may reflect the heat required to prevent condensation of the analytes in ICP torch assembly. The use of an internal standard of similar chemical structure to the analytes alleviates this problem, as illustrated by a difference of 0.3 ± 0.7‰ (1 s, n = 6) between the δ81Br values of co‐injected methoxy BDE‐47 and BDE‐47 extracted from whale blubber. Improvements in precision and accuracy may be achieved by the use of a more efficient heating of the torch assembly in conjunction with a set of internal standards that match the target compounds. Copyright © 2010 John Wiley & Sons, Ltd.
Three‐dimensional ultrasound image‐guided robotic system for accurate microwave coagulation of malignant liver tumours
Authors: Xu Jing , Jia Zhen‐zhong , Song Zhang‐jun , Yang Xiang‐dong , Chen Ken , Liang Ping
Published: June 2010

Background

The further application of conventional ultrasound (US) image‐guided microwave (MW) ablation of liver cancer is often limited by two‐dimensional (2D) imaging, inaccurate needle placement and the resulting skill requirement. The three‐dimensional (3D) image‐guided robotic‐assisted system provides an appealing alternative option, enabling the physician to perform consistent, accurate therapy with improved treatment effectiveness.

Methods

Our robotic system is constructed by integrating an imaging module, a needle‐driven robot, a MW thermal field simulation module, and surgical navigation software in a practical and user‐friendly manner. The robot executes precise needle placement based on the 3D model reconstructed from freehand‐tracked 2D B‐scans. A qualitative slice guidance method for fine registration is introduced to reduce the placement error caused by target motion. By incorporating the 3D MW specific absorption rate (SAR) model into the heat transfer equation, the MW thermal field simulation module determines the MW power level and the coagulation time for improved ablation therapy. Two types of wrists are developed for the robot: a ‘remote centre of motion’ (RCM) wrist and a non‐RCM wrist, which is preferred in real applications.

Results

The needle placement accuracies were < 3 mm for both wrists in the mechanical phantom experiment. The target accuracy for the robot with the RCM wrist was improved to 1.6 ± 1.0 mm when real‐time 2D US feedback was used in the artificial‐tissue phantom experiment. By using the slice guidance method, the robot with the non‐RCM wrist achieved accuracy of 1.8 ± 0.9 mm in the ex vivo experiment; even target motion was introduced. In the thermal field experiment, a 5.6% relative mean error was observed between the experimental coagulated neurosis volume and the simulation result.

Conclusion

The proposed robotic system holds promise to enhance the clinical performance of percutaneous MW ablation of malignant liver tumours. Copyright © 2010 John Wiley & Sons, Ltd.
Robotic‐assisted laparoscopic radical cystoprostatectomy and extracorporeal continent urinary diversion: highlight of surgical techniques and outcomes
Authors: Josephson D. Y. , Chen J. A. , Chan K. G. , Lau C. S. , Nelson R. A. , Wilson T. G.
Published: June 2010

Background

We report our technique for robotic‐assisted laparoscopic radical cystoprostatectomy (RARCP) and extracorporeal urinary diversion and present their clinical outcomes.

Methods

Between October 2003 and December 2008 we performed 58 RARCPs with extracorporeal continent urinary diversion. Preoperative, operative and postoperative data was evaluated.

Results

Mean patient age was 68 (range 46–89) years, with an average American Society of Anesthesiologists classification of 2.9. Mean operative time was 8 (range 5–11) h. Median blood loss was 450 ml. Thirteen patients received intra‐operative blood transfusions and 22 patients received peri‐operative blood transfusions. Continent urinary diversions were performed by means of the Studer technique (n = 42) or Indiana pouch (n = 16). Mean number of lymph nodes examined on lymphadenectomy was 27 (range 0–52).

Conclusions

Our RARCP and continent diversion technique is a safe and feasible option for primary urothelial carcinoma of the bladder. Oncological and surgical outcomes are comparable to open cystectomy series. Copyright © 2010 John Wiley & Sons, Ltd.
Elementary teachers' pedagogical content knowledge for teaching the nature of science
Authors: Hanuscin Deborah L. , Lee Michele H. , Akerson Valarie L.
Published: June 2010

Although teacher educators have achieved some success in improving teachers' understanding of the nature of science (NOS), helping teachers teach NOS has proved a much greater challenge. Currently, there are few examples in the literature of teachers who effectively teach NOS, and fewer still that rely on student outcomes as a measure of teachers' effectiveness. Much remains to be understood regarding the sources, nature, and development of teachers' pedagogical content knowledge (PCK) in regard to NOS. Using S. Magnusson, J. Krajcik, and H. Borko's (1999) framework, we examined the PCK for NOS of three elementary teachers who have been successful in improving their students' understanding of NOS. We relied on interviews, questionnaires, classroom observations, and classroom artifacts collected over a 3‐year period to characterize their PCK for NOS. Although each had robust knowledge of instructional strategies for teaching NOS, teachers lacked the requisite knowledge of assessment that would provide a feedback loop to support continued development of their knowledge of learners and lead to improvement in their teaching of NOS. Our findings highlight a need for professional development that focuses on developing aspects of PCK for NOS such as teachers' knowledge of assessment as well as educative curriculum materials to support continued development of teachers' PCK for NOS in practice. © 2010 Wiley Periodicals, Inc. Sci Ed 95: 145–167, 2011
Progress in the Light Emission of Colloidal Semiconductor Nanocrystals
Authors: Gaponik Nikolai , Hickey Stephen G. , Dorfs Dirk , Rogach Andrey L. , Eychmüller Alexander
Published: June 2010

Some 25 years ago it was found that semiconductor nanocrystals emitted light. Since then tremendous progress has been made with respect to increasing the emission quantum yields, extending the spectral range that may be addressed, from the UV across to the near infrared, and improving the color purity. Here some major lines in these developments are reviewed, touching on milestones as well as on the principles of the most successful preparative approaches.
Improved Biomolecule microarrays by Printing on Nanoporous Aluminum Oxide Using a Continuous‐Flow Microspotter
Authors: Kim Jungkyu , Miles Adam , Gale Bruce K.
Published: June 2010

Biomolecules, including protein A, albumin, and immunoglobulin G, are spotted on top of a nanoporous substrate by using a continuous‐flow microspotter (CFM) system, which normally produces spots 3 to 4 orders of magnitude more sensitive than conventional biomolecule printing methods. The spots are observed with a fluorescence scanner. By using the CFM to print spots on nanoporous substrates, an additional order of magnitude increase in signal is observed, which leads to high signal‐to‐background ratios, highly saturated spots, and a measurable signal at printing concentrations as low as 1.6 ng mL−1. This technique produces highly concentrated biomolecular spots from dilute samples and significantly increases the sensitivity of sensing platforms.