bluuebunny/crossref_metadata_2025 huggingface dataset:
Site‐Selected Doping of Upconversion Luminescent Er3+ into SrTiO3 for Visible‐Light‐Driven Photocatalytic H2 or O2 Evolution
Authors: Shi Jinwen , Ye Jinhua , Ma Lijing , Ouyang Shuxin , Jing Dengwei , Guo Liejin
Published: April 2012

A series of upconversion luminescent erbium‐doped SrTiO3 (ABO3‐type) photocatalysts with different initial molar ratios of Sr/Ti have been prepared by a facile polymerized complex method. Er3+ ions, which were gradually transferred from the A to the B site with increasing Sr/Ti, enabled the absorption of visible light and the generation of high‐energy excited states populated by upconversion processes. The local internal fields arising from the dipole moments of the distorted BO6 octahedra promoted energy transfer from the high‐energy excited states of Er3+ with B‐site occupancy to the host SrTiO3 and thus enhanced the band‐to‐band transition of the host SrTiO3. Consequently, the erbium‐doped SrTiO3 species with B‐site occupancy showed higher photocatalytic activity than those with A‐site occupancy for visible‐light‐driven H2 or O2 evolution in the presence of the corresponding sacrificial reagents. The results generally suggest that the introduction of upconversion luminescent agents into host semiconductors is a promising approach to simultaneously harnessing low‐energy photons and maintaining redox ability for photocatalytic H2 and O2 evolution and that the site occupancy of doped elements in ABO3‐type perovskite oxides greatly determines the photocatalytic activity.
Axial Ligand and Spin‐State Influence on the Formation and Reactivity of Hydroperoxo–Iron(III) Porphyrin Complexes
Authors: Franke Alicja , Fertinger Christoph , van Eldik Rudi
Published: April 2012

The present study focuses on the formation and reactivity of hydroperoxo–iron(III) porphyrin complexes formed in the [FeIII(tpfpp)X]/H2O2/HOO− system (TPFPP=5,10,15,20‐tetrakis(pentafluorophenyl)‐21H,23H‐porphyrin; X=Cl− or CF3SO3−) in acetonitrile under basic conditions at −15 °C. Depending on the selected reaction conditions and the active form of the catalyst, the formation of high‐spin [FeIII(tpfpp)(OOH)] and low‐spin [FeIII(tpfpp)(OH)(OOH)] could be observed with the application of a low‐temperature rapid‐scan UV/Vis spectroscopic technique. Axial ligation and the spin state of the iron(III) center control the mode of OO bond cleavage in the corresponding hydroperoxo porphyrin species. A mechanistic changeover from homo‐ to heterolytic OO bond cleavage is observed for high‐ [FeIII(tpfpp)(OOH)] and low‐spin [FeIII(tpfpp)(OH)(OOH)] complexes, respectively. In contrast to other iron(III) hydroperoxo complexes with electron‐rich porphyrin ligands, electron‐deficient [FeIII(tpfpp)(OH)(OOH)] was stable under relatively mild conditions and could therefore be investigated directly in the oxygenation reactions of selected organic substrates. The very low reactivity of [FeIII(tpfpp)(OH)(OOH)] towards organic substrates implied that the ferric hydroperoxo intermediate must be a very sluggish oxidant compared with the iron(IV)–oxo porphyrin π‐cation radical intermediate in the catalytic oxygenation reactions of cytochrome P450.
Silicon‐Containing Formal 4π‐Electron Four‐Membered Ring Systems: Antiaromatic, Aromatic, or Nonaromatic?
Authors: Yang Yun‐Fang , Cheng Gui‐Juan , Zhu Jun , Zhang Xinhao , Inoue Shigeyoshi , Wu Yun‐Dong
Published: April 2012

Density functional theory calculations (B3LYP) have been carried out to investigate the 4π‐electron systems of 2,4‐disila‐1,3‐diphosphacyclobutadiene (compound 1) and the tetrasilacyclobutadiene dication (compound 2). The calculated nucleus‐independent chemical shift (NICS) values for these two compounds are negative, which indicates that the core rings of compounds 1 and 2 have a certain amount of aromaticity. However, deep electronic analysis reveals that neither of these two formal 4π‐electron four‐membered ring systems is aromatic. Compound 1 has very weak, almost negligible antiaromaticity, and the amidinate ligands attached to the Si atoms play an important role in stabilizing this conjugated 4π‐electron system. The monoanionic bidentate ligand interacts with the conjugated π system to cause π‐orbital splitting. This ligand‐induced π‐orbital splitting effect provides an opportunity to manipulate the gap between occupied and unoccupied π orbitals in conjugated systems. Conversely, compound 2 is nonaromatic because its core ring does not have a conjugated π ring system and does not fulfill the requirements of a Hückel system.
Additional Base‐Pair Formation in DNA Duplexes by a Double‐Headed Nucleotide
Authors: Madsen Charlotte S. , Witzke Sarah , Kumar Pawan , Negi Kushuma , Sharma Pawan K. , Petersen Michael , Nielsen Poul
Published: April 2012

We have designed and synthesised a double‐headed nucleotide that presents two nucleobases in the interior of a dsDNA duplex. This nucleotide recognises and forms Watson–Crick base pairs with two complementary adenosines in a Watson–Crick framework. Furthermore, with judicious positioning in complementary strands, the nucleotide recognises itself through the formation of a T:T base pair. Thus, two novel nucleic acid motifs can be defined by using our double‐headed nucleotide. Both motifs were characterised by UV melting experiments, CD and NMR spectroscopy and molecular dynamics simulations. Both motifs leave the thermostability of the native dsDNA duplex largely unaltered. Molecular dynamics calculations showed that the double‐headed nucleotides are accommodated in the dsDNA by entirely local perturbations and that the modified duplexes retain an overall B‐type geometry with the dsDNA unwound by around 25 or 60°, respectively, in each of the modified motifs. Both motifs can be accommodated twice in a dsDNA duplex without incurring any loss of stability and extrapolating from this observation and the results of modelling, it is conceivable that both can be multiplied several times within a dsDNA duplex. These new motifs extend the DNA recognition repertoire and may form the basis for a complete series of double‐headed nucleotides based on all 16 base combinations of the four natural nucleobases. In addition, both motifs can be used in the design of nanoscale DNA structures in which a specific duplex twist is required.
Computational Design of Cyclic Nitroxides as Efficient Redox Mediators for Dye‐Sensitized Solar Cells
Authors: Gryn'ova Ganna , Barakat Jonathan M. , Blinco James P. , Bottle Steven E. , Coote Michelle L.
Published: April 2012

Cyclic nitroxide radicals represent promising alternatives to the iodine‐based redox mediator commonly used in dye‐sensitized solar cells (DSSCs). To date DSSCs with nitroxide‐based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one‐electron oxidation and it must possess an oxidation potential in a range of 0.600–0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N‐containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl‐, methoxy‐, amino‐, carboxy‐, etc.) to the ring. Standard oxidation potentials were calculated using high‐level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired , and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs.
Enantioselective Synthesis of anti‐β‐Hydroxy‐α‐Amido Esters by Asymmetric Transfer Hydrogenation in Emulsions
Authors: Seashore‐Ludlow Brinton , Villo Piret , Somfai Peter
Published: April 2012

Herein, we present two methods for an asymmetric transfer hydrogenation through the dynamic kinetic resolution of α‐amido‐β‐ketoesters. These procedures yield the corresponding anti‐β‐hydroxy‐α‐amido esters in good yields and with good diastereo‐ and enantioselectivities. First, the scope of the reduction of α‐amido‐β‐ketoesters by using triethylammonium formate azeotrope is examined. Then, an emulsion technology with sodium formate is explored, which allows for broader substrate scope, faster reaction times, and lower catalyst loading. Furthermore, these reactions are operationally simple and can be set up in air.
Electrochemiluminescent Determination of Cancer Cells Based on Aptamers, Nanoparticles, and Magnetic Beads
Authors: Ding Caifeng , Wei Shuang , Liu Haitao
Published: April 2012

Herein we report a polymerase chain reaction (PCR)‐free electrochemiluminescence (ECL) approach that uses ECL nanoprobes for the determination of cancer cells with high sensitivity. The ECL nanoprobe consists of gold nanoparticles (AuNPs), linker DNA, and tris(2,2′‐bipyridyl)ruthenium (TBR)‐labeled signal DNA. The linker DNA and signal DNA were modified on the surface of the AuNPs through AuS bonds. The linker DNA can partly hybridize with the aptamers of cancer cells loaded onto the magnetic beads (MB1) to construct the magnetic biocomplexes. In the presence of the cancer cells, the aptamers conjugated with the cancer cells with higher affinity. The ECL nanoprobe was released from the biocomplexes and subsequently hybridized with the capture DNA loaded onto another magnetic bead (MB2) to form the magnetic nanocomposite. The nanocomposites can be easily separated and firmly attached to an electrode on account of their excellent magnetic properties. The ECL intensity of the TBR loaded onto the nanocomposites directly reflected the amount of cancer cells. By using cell lines of Burkitt’s lymphoma (Ramos cells) as a model, the ECL response was proportional to the cell concentration in the range from 5 to 100 cells ml−1; a limit of detection as low as 5 cells ml−1 of Ramos cells could be achieved. The proposed method described here is ideal for the diagnosis of cancers due to its high sensitivity, simplicity, and low cost.
En Route to Dinitroacetylene: Nitro(trimethylsilyl)acetylene and Nitroacetylene Harnessed by Dicobalt Hexacarbonyl
Authors: Windler G. Kenneth , Zhang Mao‐Xi , Zitterbart Robert , Pagoria Philip F. , Vollhardt K. Peter C.
Published: April 2012

Dinitroacetylene and other nitroacetylenes are attractive stoichiometric precursors to high energy‐density materials, but suffer from high reactivity and thermal instability. Herein, we report that nitroacetylenes can be dramatically stabilized in the form of their dicobalt hexacarbonyl complexes. In particular, we describe the syntheses and characterization of the first two transition‐metal complexes of nitroalkynes, [μ‐1‐nitro‐2‐(trimethylsilyl)ethyne‐1,2‐diyl]bis(tricarbonylcobalt)(Co—Co) and [μ‐1‐nitroethyne‐1,2‐diyl]bis(tricarbonylcobalt)(Co—Co). The chemistry of these compounds reveals their potential as reaction partners in [2+2+2] cyclotrimerizations, furnishing nitroindane, nitrotetralin, and trinitrobenzene products. The X‐ray crystal structure of 1,3,5‐trinitro‐2,4,6‐tris(trimethylsilyl)benzene presents a distorted, yet planar, aromatic ring.
Plant Extraction: Key Technology for Sustained Use of Bio‐Resources
Authors: Tegtmeier Martin
Published: April 2012

Seit Beginn der Zivilisation gehören Pflanzen zu den wichtigsten Alltagsgegenständen für den Menschen. Schon bald werden Pflanzen nicht nur eine direkte Nahrungsquelle sondern auch Basis für die Herstellung und Bereitstellung vieler im täglichen Leben benötigter Utensilien sein. Die Verarbeitung von Pflanzen erfordert dabei immer weiter entwickelte Fertigkeiten, um wachsende Bedürfnisse zu erfüllen. Mit der Nutzung von abgetrennten Pflanzenbestandteilen, vornehmlich von ausgewählten Inhaltsstofffraktionen, wurden die Kenntnisse zur Extraktion weiterentwickelt. Das fortschreitende Wissen zur Materialkunde und zur Mechanisierung führte zur Etablierung von Extraktionsverfahren, die die kontinuierliche Herstellung von qualitativ hochwertigen Produkten gewährleisten. Diese Phase markiert auch den Ursprung der Phytotechnologie als eigenständige wissenschaftliche und technische Disziplin zur Extraktion von Pflanzen.
Health Risk Assessment for Arsenic in Water Sources of Cankiri Province of Turkey
Authors: Caylak Emrah
Published: April 2012

To investigate the levels of arsenic (As) in the water sources of Cankiri Province, the samples were collected from the stations of central Cankiri (n = 27) and Kursunlu town (n = 12) during 2009 and 2010. The concentrations of As were analyzed with an atomic absorption spectrophotometer, and then compared with permissible limit, 10 µg/L in drinking water, by Turkish legislation and World Health Organization (WHO). The As levels were higher than this limit (mean value 10–30 µg/L in 26 stations), whereas, they were found to be >30 µg/L in 12 sampling points. The water sources were categorized for health risk assessment such as reservoir, tap, well, and spring, and then chronic daily intake for oral and dermal exposure to As via drinking water, hazard quotient (HQ), and hazard index were calculated by using indices. The HQ values were found to be >1 in all samples of Cankiri Province. The effects of As on human health were then evaluated using carcinogenic risk (CR). CR values for As were also estimated to be >10−5 in drinking water samples of Cankiri Province and might exert potential CR for people. These assessments would point out required drinking water treatment strategy to ensure safety of consumers.
Ultrafast Photoinduced Electron Transfer at Electrodes: The General Case of a Heterogeneous Electron‐Transfer Reaction
Authors: Gundlach Lars , Willig Frank
Published: April 2012

The general case of a heterogeneous electron‐transfer reaction is realized by ultrafast electron transfer from a light‐absorbing molecule to a wide continuum of electronic acceptor states, realizing the so‐called wide band limit. Experimental data obtained for perylene dye/TiO2 systems confirm the predictions of fully quantum mechanical model calculations of the dynamics. The energy distribution of the injected electron shows an energy loss due to excitations of high‐energy (quantum) vibrational modes in the ionized perylene moiety. The electron‐transfer mechanism is non‐adiabatic and the reaction is ultrafast, for example, with a time constant of 9 fs for the COOH anchor‐bridge group. The underlying strong coupling of the electronic states to high‐energy vibrational modes is a characteristic feature of sensitizer molecules.
Firefly Chemiluminescence and Bioluminescence: Efficient Generation of Excited States
Authors: Pinto da Silva Luís , Esteves da Silva Joaquim C. G.
Published: April 2012

Firefly luciferase catalyzes a light‐emitting reaction in which an excited‐state product is formed. Both experimental and theoretical methodologies are used to study this system, and the reactions catalyzed by luciferase are relatively well characterized. However, the mechanism by which an excited‐state product is formed is still unknown. This Minireview deals with the current understanding of firefly bioluminescence and chemiluminescence. Thermal decomposition of simple 1,2‐dioxetanes is also discussed, due to their role in formation of the excited‐state bioluminophore.
Multiple phosphorylation sites are important for RUNX1 activity in early hematopoiesis and T‐cell differentiation
Authors: Yoshimi Mayumi , Goyama Susumu , Kawazu Masahito , Nakagawa Masahiro , Ichikawa Motoshi , Imai Yoichi , Kumano Keiki , Asai Takashi , Mulloy James C. , Kraft Andrew S. , Takahashi Tsuyoshi , Shirafuji Naoki , Kurokawa Mineo
Published: April 2012

RUNX1 is essential for definitive hematopoiesis and T‐cell differentiation. It has been shown that RUNX1 is phosphorylated at specific serine and threonine residues by several kinase families. However, it remains unclear whether RUNX1 phosphorylation is absolutely required for its biological functions. Here, we evaluated hematopoietic activities of RUNX1 mutants with serine (S)/threonine (T) to alanine (A), aspartic acid (D), or glutamic acid (E) mutations at phosphorylation sites using primary culture systems. Consistent with the results of knockin mice, RUNX1‐2A, carrying two phospho‐deficient mutations at S276 and S293, retained hematopoietic activity. RUNX1‐4A, carrying four mutations at S276, S293, T300, and S303, showed impaired T‐cell differentiation activity, but retained the ability to rescue the defective early hematopoiesis of Runx1‐deficient cells. Notably, RUNX1‐5A, carrying five mutations at S276, S293, T300, S303, and S462, completely lost its hematopoietic activity. In contrast, the phospho‐mimic proteins RUNX1‐4D/E and RUNX1‐5D/E exhibited normal function. Our study identifies multiple phosphorylation sites that are indispensable for RUNX1 activity in hematopoiesis.
Immunoglobulin class switching appears to be regulated by B‐cell antigen receptor‐specific T‐cell action
Authors: Lange Hans , Hecht Oliver , Zemlin Michael , Trad Ahmad , Tanasa Radu I. , Schroeder Harry W. , Lemke Hilmar
Published: April 2012

Antigen affinity is commonly viewed as the driving force behind the selection for dominant clonotypes that can occur during the T‐cell‐dependent processes of class switch recombination (CSR) and immune maturation. To test this view, we analyzed the variable gene repertoires of natural monoclonal antibodies to the hapten 2‐phenyloxazolone (phOx) as well as those generated after phOx protein carrier‐induced thymus‐dependent or Ficoll‐induced thymus‐independent antigen stimulation. In contrast to expectations, the extent of IgM heterogeneity proved similar and many IgM from these three populations exhibited similar or even greater affinities than the classic Ox1 clonotype that dominates only after CSR among primary and memory IgG. The population of clones that were selected during CSR exhibited a reduced VH/VL repertoire that was enriched for variable domains with shorter and more uniform CDR‐H3 lengths and almost completely stripped of variable domains encoded by the large VH1 family. Thus, contrary to the current paradigm, T‐cell‐dependent clonal selection during CSR appeared to select for VH family and CDR‐H3 loop content even when the affinity provided by alternative clones exhibited similar to increased affinity for antigen.
CBA/J mice generate protective immunity to soluble Ag85 but fail to respond efficiently to Ag85 during natural Mycobacterium tuberculosis infection
Authors: Beamer Gillian L. , Cyktor Joshua , Flaherty David K. , Stromberg Paul C. , Carruthers Bridget , Turner Joanne
Published: April 2012

In CBA/J mice, susceptibility to Mycobacterium tuberculosis (M.tb) is associated with low interferon‐gamma (IFN‐γ) responses to antigens (Antigen 85 (Ag85) and early secreted antigenic target‐6 (ESAT‐6)) that have been defined as immunodominant. Here, we asked whether the failure of CBA/J mice to recognize Ag85 is a consequence of M.tb infection or whether CBA/J mice have a general defect in generating specific T‐cell responses to this protein antigen. We compared CBA/J mice during primary M.tb infection, Ag85 vaccination followed by M.tb challenge, or M.tb memory immune mice for their capacity to generate Ag85‐specific IFN‐γ responses and to control M.tb infection. CBA/J mice did not respond efficiently to Ag85 in the context of natural infection or re‐infection. In contrast, CBA/J mice could generate Ag85‐specific IFN‐γ responses and protective immunity when this antigen was delivered as a soluble protein. Our data indicate that although M.tb infection of CBA/J mice does not drive an Ag85 response, these mice can fully and protectively respond to Ag85 if it is delivered as a vaccine. The data from this experimental model suggest that the Ag85‐containing vaccines in clinical trials should protect M.tb susceptible humans.
Complement plays a central role in Candida albicans‐induced cytokine production by human PBMCs
Authors: Cheng Shih‐Chin , Sprong Tom , Joosten Leo A.B. , van der Meer Jos W. M. , Kullberg Bart‐Jan , Hube Bernhard , Schejbel Lone , Garred Peter , van Deuren Marcel , Netea Mihai G.
Published: April 2012

In experimental studies, the role of complement in antifungal host defense has been attributed to its opsonizing capability. In this study, we report that in humans an activated complement system mainly augments Candida albicans‐induced host proinflammatory cytokine production via C5a‐C5aR signaling, while phagocytosis and intracellular killing of Candida are not influenced. By blocking the C5a‐C5aR signaling pathway, either with anti‐C5a antagonist antibodies or with the C5aR antagonist W‐54001, C. albicans‐induced IL‐6 and IL‐1β levels were significantly reduced. Recombinant C5a augmented cytokine production. In addition, using serum from patients with various complement deficiencies, we demonstrated a crucial role of C5, but not C6 or the membrane attack complex, in C. albicans‐induced IL‐6 and IL‐1β production in monocytes. These findings reveal a central role of anaphylatoxin C5a in augmenting host proinflammatory cytokine production upon contact with C. albicans, and define the role of the complement system in anti‐Candida host defense in humans.
Targeting of macrophage galactose‐type C‐type lectin (MGL) induces DC signaling and activation
Authors: Napoletano Chiara , Zizzari Ilaria G. , Rughetti Aurelia , Rahimi Hassan , Irimura Tatsuro , Clausen Henrik , Wandall Hans H. , Belleudi Francesca , Bellati Filippo , Pierelli Luca , Frati Luigi , Nuti Marianna
Published: April 2012

Dendritic cells (DCs) sense the microenvironment through several types of receptors recognizing pathogen‐associated molecular patterns. In particular, C‐type lectins, expressed by distinct subsets of DCs, recognize and internalize specific carbohydrate antigen in a Ca2+‐dependent manner. Targeting of these receptors is becoming an efficient strategy of delivering antigens in DC‐based anticancer immunotherapy. Here we investigated the role of the macrophage galactose type C‐lectin receptor (MGL), expressed by immature DCs (iDCs), as a molecular target for α‐N‐acetylgalactosamine (GalNAc or Tn)‐carrying tumor‐associated antigens to improve DC performance. MGL expressed by ex vivo‐generated iDCs from healthy donors was engaged by a 60‐mer MUC19Tn‐glycopeptide as a Tn‐carrying tumor‐associated antigen, and an anti‐MGL antibody, as a specific MGL binder. We demonstrated that MGL engagement induced homotrimers and homodimers, triggering the phosphorylation of extracellular signal‐regulated kinase 1,2 (ERK1,2) and nuclear factor‐κB activation. Analysis of DC phenotype and function demonstrated that MGL engagement improved DC performance as antigen‐presenting cells, promoting the upregulation of maturation markers, a decrease in phagocytosis, an enhancement of motility, and most importantly an increase in antigen‐specific CD8+ T‐cell activation. These results demonstrate that the targeting of MGL receptor on human DCs has an adjuvant effect and that this strategy can be used to design novel anticancer vaccines.
Production of different proteases from fish gut microflora utilizing tannery fleshing
Authors: Sumathi Chellappan , Mohanapriya Dhanasekaran , Mandal Asit Baran , Sekaran Ganesan
Published: April 2012

Three alkaline protease‐producing strains designated as ANFLR1, NPLR1, and PROLR15 were isolated from Labeo rohita fish gut. These strains are able to produce alkaline protease using tannery fleshing (TF) as the sole carbon and nitrogen source and were identified as Bacillus megaterium, Serratia marcescens, and novel Pontibacter sps. Proteases from these organisms were purified to electrophoretic homogeneity following ammonium sulphate precipitation, ion exchange, and column chromatography. SDS‐PAGE revealed molecular weights of the proteases to be 46 kDa (ANFLR1), 52 kDa (NPLR1), and 58 kDa (PROLR15). The optimum pH and temperature for the protease activity of ANFLR1, NPLR1, and PROLR15 were found to be 10.5, 11.5, 9, and 70°C, 60°C, and 50°C, respectively. The maximum protease activities at the optimum conditions were 420 U/mL (ANFLR1), 550 U/mL (NPLR1), and 530 U/mL (PROLR15). Inhibition of the NPLR1 protease by pepstatin confirmed aspartate‐type enzymatic activity. Fe3+ enhanced the activity of PROLR15 protease. Unlike all other microbial proteases known so far, the PROLR15 enzyme did not require Ca2+ for activity and thermal stability. SDS‐PAGE and scanning electron microscopy analyses confirmed the conversion of high molecular weight substrate (TF) to low molecular weight peptides by these proteases. The alkaline metalloprotease production by novel Pontibacter sps. and aspartate protease production by S. marcescens remain unexplored. Hence, TF with its relatively abundant availability can be beneficially utilized for alkaline protease production through the fish gut microbial fermentation processes.
Mitigating Product Hazards via User Warnings Alone: When/Why “Warnings‐Only” Approaches Are Likely to Fail
Authors: Lenorovitz David R. , Karnes Edward W. , Leonard S. David
Published: April 2012

Some products may involve hazards in their use. Manufacturers are obligated to evaluate such hazards and to abate them according to a hierarchy of hazard control approaches, namely, 1) to design them out, 2) to shield users from their effects, or 3) to adequately warn users of their danger(s). Warnings are last in this hierarchy because they provide a lesser guarantee of success. Additionally, warnings developed for this purpose may be inadequate because of a variety of factors, including the warning's clarity/understandability, its high cost of compliance, the need for responses beyond the users' capabilities, the need for unavailable or difficult‐to‐use protective equipment, or asking users to perform actions contrary to previously learned or innately reactive behaviors. This article describes problems with three types of vehicles that contained known hazards—where the manufacturer relied solely on product warnings to mitigate that hazard, and, in turn, provided warnings that were inadequate for one or more of these reasons. © 2012 Wiley Periodicals, Inc.
Interfering with Fos expression in rat perirhinal cortex impairs recognition memory
Authors: Seoane Ana , Tinsley Christopher J. , Brown Malcolm W.
Published: April 2012

Previous work has shown that immunohistochemical imaging of Fos protein is a reliable marker for changes in activity related to recognition memory in the perirhinal (PRH) cortex of the medial temporal lobe; however, whether PRH Fos expression is necessary for recognition memory had not been established. To investigate this potential requirement, antisense Fos oligodeoxynucleotide (ODN) was infused locally into PRH cortex to interfere with Fos production. As in previous studies, differential Fos expression produced by viewing novel or familiar visual stimuli was measured by immunohistochemistry: antisense Fos ODN infusion into PRH cortex disrupted the normal pattern of differential Fos expression in PRH cortex. The effect of antisense Fos ODN infusion into PRH cortex was therefore sought on recognition memory. Infusion before or immediately after acquisition impaired recognition memory for objects when the memory delay was 3 or 24 h, but not when the delay was 20 min, or when the ODN was infused before retrieval after a 24‐h delay. The findings indicate a role for Fos in consolidation processes underlying long‐term recognition memory for objects and establish that interfering with its expression impairs recognition memory. Antisense Fos ODN infusion also impaired object‐in‐place recognition memory. The results demonstrate that Fos is necessary for neuronal mechanisms in PRH cortex essential to recognition memory. © 2012 Wiley Periodicals, Inc.
Delineation of saltwater intrusion zones using the time domain electromagnetic method: the Nabeul–Hammamet coastal aquifer case study (NE Tunisia)
Authors: Trabelsi Fatma , Mammou Abdallah Ben , Tarhouni Jamila , Piga Carlo , Ranieri Gaetano
Published: April 2012

The time domain electromagnetic method (TDEM) is applied to monitor, to delineate and to map the saltwater intrusion zones in the Mediterranean Plio‐Quaternary aquifer. Forty‐two TDEM soundings were carried out in the coastal plain of Nabeul–Hammamet region (NE Tunisia). TDEM resistivity data were correlated with the existing borehole logging data to assign them to a particular lithology and to provide information about the position of the freshwater–seawater transition zone. The geoelectric sections showing the vertical configuration of seawater intrusion, with the brackish‐salty‐saturated zones, have a resistivity ranging from ~0.1 to 5 Ω⋅m and are detected at a depth lower than 1.5 m. The salinized zones are located at Nabeul (Sidi Moussa, Sidi El Mahrsi, Al Gasba and Mrazgua) and at Hammamet (Touristic zone of Hammamet north and south, Baraket Essahel) and reached a distance of 4 km from the coastline, indicating a severe state for the aquifer in these zones. These TDEM results are confirmed by the increase of chloride concentration content in the analysed water samples of monitoring wells. Moreover, in the northeastern part, the presence of a saltwater front located far from the coast and along the NW–SE major surface fault can be explained by two hypothesis: (i) this fault seems to provide a conduit for seawater to move readily towards the water wells and (ii) the clay and gypsum infiltration of marine Messinian deposits through the fault plane leads to low resistivities. Finally, it comes out from this study that TDEM survey has successfully depicted salinized zones of this coastal aquifer. Copyright © 2012 John Wiley & Sons, Ltd.
Discrete wavelet‐based trend identification in hydrologic time series
Authors: Sang Yan‐Fang , Wang Zhonggen , Liu Changming
Published: April 2012

Trend identification is a substantial issue in hydrologic series analysis, but it is also a difficult task in practice due to the confusing concept of trend and disadvantages of methods. In this article, an improved definition of trend was given as follows: ‘a trend is the deterministic component in the analysed data and corresponds to the biggest temporal scale on the condition of giving the concerned temporal scale’. It emphasizes the intrinsic and deterministic properties of trend, can clearly distinguish trend from periodicities and points out the prerequisite of the concerned temporal scale only by giving which the trend has its specific meaning. Correspondingly, the discrete wavelet‐based method for trend identification was improved. Differing from those methods used presently, the improved method is to identify trend by comparing the energy difference between hydrologic data and noise, and it can simultaneously separate periodicities and noise. Furthermore, the improved method can quantitatively estimate the statistical significance of the identified trend by using proper confidence interval. Analyses of both synthetic and observed series indicated the identical power of the improved method as the Mann–Kendall test in assessing the statistical significance of the trend in hydrologic data, and by using the former, the identified trend can adaptively reflect the nonlinear and nonstationary variability of hydrologic data. Besides, the results also showed the influences of three key factors (wavelet choice, decomposition level choice and noise content) on discrete wavelet‐based trend identification; hence, they should be carefully considered in practice. Copyright © 2012 John Wiley & Sons, Ltd.
Characteristics of canopy interception loss in Moso bamboo forests of Japan
Authors: Shinohara Yoshinori , Komatsu Hikaru , Kuramoto Kohei , Otsuki Kyoichi
Published: April 2012

In recent years, Moso bamboo (Phyllostachys pubescens) forests have rapidly expanded in Japan by replacing surrounding coniferous and/or broadleaved forests. To evaluate the change in water yield from forested areas because of this replacement, it is necessary to examine evapotranspiration for Moso bamboo forests. However, canopy interception loss, one of the major components of evapotranspiration in forested areas, has been observed in only two Moso bamboo forests in Japan with relatively high stem density (~7000 stems/ha). There are, in fact, many Moso bamboo forests with much lower stem density. Thus, we made precipitation (Pr), throughfall (Tf) and stemflow (Sf) observations for 1 year in a Moso bamboo forest with stem density of 3611 stems/ha and quantified canopy interception loss (Ic). Pr and Ic for the experimental period were 1636 and 166 mm, respectively, and Ic/Pr was 10%. The value was approximately the same as values for the other two Moso bamboo forests and lower than values for coniferous and broadleaved forests. On the other hand, Tf/Pr and Sf/Pr for our forest (86% and 4%, respectively) were approximately 10% of Pr larger and smaller than values for the other two Moso bamboo forests. These results suggest that the difference in stem density greatly affects precipitation partitioning (i.e. Tf/Pr and Sf/Pr) but does not greatly change Ic/Pr. Copyright © 2012 John Wiley & Sons, Ltd.
Quantifying watershed surface depression storage: determination and application in a hydrologic model
Authors: Amoah Joseph K. O. , Amatya Devendra M. , Nnaji Soronnadi
Published: April 2012

Hydrologic models often require correct estimates of surface macro‐depressional storage to accurately simulate rainfall–runoff processes. Traditionally, depression storage is determined through model calibration or lumped with soil storage components or on an ad hoc basis. This paper investigates a holistic approach for estimating surface depressional storage capacity (DSC) in watersheds using digital elevation models (DEMs). The methodology includes implementing a lumped DSC model to extract geometric properties of storage elements from DEMs of varying grid resolutions and employing a consistency zone criterion to quantify the representative DSC of an isolated watershed. DSC obtained using the consistency zone approach is compared to DSC estimated by “brute force” (BF) optimization method. The BF procedure estimates optimal DSC by calibrating DRAINMOD, a quasi‐process based hydrologic model, with observed streamflow under different climatic conditions. Both methods are applied to determine the DSC for relatively low‐gradient coastal plain watersheds on forested landscape with slopes less than 3%. Results show robustness of the consistency zone approach for estimating depression storage. To test the adequacy of the calculated DSC values obtained, both methods are applied in DRAINMOD to predict the daily watershed flow rates. Comparison between observed and simulated streamflow reveals a marginal difference in performance between BF optimization and consistency zone estimated DSCs during wet periods, but the latter performed relatively better in dry periods. DSC is found to be dependent on seasonal antecedent moisture conditions on surface topography. The new methodology is beneficial in situations where data on depressional storage is unavailable for calibrating models requiring this input parameter. Copyright © 2012 John Wiley & Sons, Ltd.
Parental involvement in home visiting: Interpersonal predictors and correlates
Authors: Sierau Susan , Brand Tilman , Jungmann Tanja
Published: April 2012

Parents' commitment to and usage of early intervention are key variables in understanding discrepancies in families' susceptibility to these services. Although the important role of fathers in infant development is widely recognized, early interpersonal predictors of paternal involvement in home‐visiting programs have been understudied. This article aims to fill this gap by regressing parents' postnatal involvement on prenatal partnership satisfaction and quality of the helping relationship in a sample of 124 socially and financially disadvantaged families. Paternal program engagement was predicted by partnership satisfaction whereas the perceived quality of the helping relationship best predicted maternal program engagement, with demographical characteristics controlled. Maternal program engagement also mediated the relationship between partnership satisfaction and paternal program engagement. The results are discussed against the theoretical background.
Tumor-induced osteomalacia: An important cause of adult-onset hypophosphatemic osteomalacia in China: Report of 39 cases and review of the literature
Authors: Jiang Yan , Xia Wei-bo , Xing Xiao-ping , Silva Barbara C , Li Mei , Wang Ou , Zhang Hua-bing , Li Fang , Jing Hong-li , Zhong Ding-rong , Jin Jin , Gao Peng , Zhou Lian , Qi Fang , Yu Wei , Bilezikian John P , Meng Xun-wu
Published: April 2012

Tumor-induced osteomalacia (TIO) is an acquired form of hypophosphatemia. Tumor resection leads to cure. We investigated the clinical characteristics of TIO, diagnostic methods, and course after tumor resection in Beijing, China, and compared them with 269 previous published reports of TIO. A total of 94 patients with adult-onset hypophosphatemic osteomalacia were seen over a 6-year period (January, 2004 to May, 2010) in Peking Union Medical College Hospital. After physical examination (PE), all patients underwent technetium-99m octreotide scintigraphy (99Tcm-OCT). Tumors were removed after localization. The results demonstrated that 46 of 94 hypophosphatemic osteomalacia patients had high uptake in 99Tcm-OCT imaging. Forty of them underwent tumor resection with the TIO diagnosis established in 37 patients. In 2 patients, the tumor was discovered on PE but not by 99Tcm-OCT. The gender distribution was equal (M/F = 19/20). Average age was 42 ± 14 years. In 35 patients (90%), the serum phosphorus concentration returned to normal in 5.5 ± 3.0 days after tumor resection. Most of the tumors (85%) were classified as phosphaturic mesenchymal tumor (PMT) or mixed connective tissue variant (PMTMCT). Recurrence of disease was suggested in 3 patients (9%). When combined with the 269 cases reported in the literature, the mean age and sex distribution were similar. The tumors were of bone (40%) and soft tissue (55%) origins, with 42% of the tumors being found in the lower extremities. In summary, TIO is an important cause of adult-onset hypophosphatemia in China. 99Tcm-OCT imaging successfully localized the tumor in the overwhelming majority of patients. Successful removal of tumors leads to cure in most cases, but recurrence should be sought by long-term follow-up. © 2012 American Society for Bone and Mineral Research.
The amount of periosteal apposition required to maintain bone strength during aging depends on adult bone morphology and tissue-modulus degradation rate
Authors: Jepsen Karl J , Andarawis-Puri Nelly
Published: April 2012

Although the continued periosteal apposition that accompanies age-related bone loss is a biomechanically critical target for prophylactic treatment of bone fragility, the magnitude of periosteal expansion required to maintain strength during aging has not been established. A new model for predicting periosteal apposition rate for men and women was developed to better understand the complex, nonlinear interactions that exist among bone morphology, tissue-modulus, and aging. Periosteal apposition rate varied up to eightfold across bone sizes, and this depended on the relationship between cortical area and total area, which varies with external size and among anatomical sites. Increasing tissue-modulus degradation rate from 0% to −4%/decade resulted in 65% to 145% increases in periosteal apposition rate beyond that expected for bone loss alone. Periosteal apposition rate had to increase as much as 350% over time to maintain stiffness for slender diaphyses, whereas robust bones required less than a 32% increase over time. Small changes in the amount of bone accrued during growth (ie, adult cortical area) affected periosteal apposition rate of slender bones to a much greater extent compared to robust bones. This outcome suggested that impaired bone growth places a heavy burden on the biological activity required to maintain stiffness with aging. Finally, sex-specific differences in periosteal apposition were attributable in part to differences in bone size between the two populations. The results indicated that a substantial proportion of the variation in periosteal expansion required to maintain bone strength during aging can be attributed to the natural variation in adult bone width. Efforts to identify factors contributing to variation in periosteal expansion will benefit from developing a better understanding of how to adjust clinical data to differentiate the biological responses attributable to size-effects from other genetic and environmental factors. © 2012 American Society for Bone and Mineral Research.
Oral alendronate use and risk of cancer in postmenopausal women with osteoporosis: A nationwide study
Authors: Chiang Chia-Hung , Huang Chin-Chou , Chan Wan-Leong , Huang Po-Hsun , Chen Tzeng-Ji , Chung Chia-Min , Lin Shing-Jong , Chen Jaw-Wen , Leu Hsin-Bang
Published: April 2012

The association between use of oral bisphosphonates and cancer development in elderly women is still uncertain, and previous studies have shown controversial results. We used a nationwide, population-based database to explore the relationship between the use of alendronate, an oral bisphosphonate agent used for the treatment of osteoporosis, and the risk of all malignancies in women with osteoporosis and age over 55 years. In the study group, we included 6906 women with osteoporosis (age, mean ± SD, 73.4 ± 8.4 years) taking oral alendronate, who were selected from a 1,000,000 sample cohort dataset collected between January 1998 and December 2009. Another 20,697 age- and comorbidity-matched women (73.5 ± 8.4 years) without bisphosphonates treatment were included in the control group. No subjects had any history of being diagnosed with cancer before inclusion. We used a log-rank test to analyze the differences in accumulated cancer-free survival rates between these two groups. A Cox proportional-hazard model, adjusted for confounding factors, was used to evaluate the association between alendronate use and the development of all cancer events in postmenopausal women with osteoporosis. During the mean follow-up period of 4.8 years, 821 patients from the study group and 2646 patients from the control group had new cancers. There was no significant difference in cancer incidence between alendronate users and controls (11.9% versus 12.8%, p = 0.054). The person-year incidence of newly-developed cancer in alendronate users and controls was 28.0 and 29.4 per 1000 person-years, respectively. Alendronate use was not associated with increased risk of cancer development in women with osteoporosis (adjusted hazard ratio, 1.05; 95% confidence interval [CI], 0.97–1.13; p = 0.237). However, due to the limited study size and underpowered results, further larger prospective studies or meta-analysis are suggested to further confirm our findings. © 2012 American Society for Bone and Mineral Research.
Repeatability of edited lactate and other metabolites in astrocytoma at 3T
Authors: McLean Mary A. , Sun Amy , Bradstreet Thomas E. , Schaeffer Andrea K. , Liu Haiying , Iannone Robert , Herman Gary , Railkar Radha A. , Joubert Ilse , Gillard Jonathan H. , Price Stephen J. , Griffiths John R.
Published: April 2012

Purpose:

To assess the repeatability of measurement of lactate and other metabolites in tumors using magnetic resonance spectroscopy (MRS).

Materials and Methods:

MRS with spectral editing for lactate was performed on 10 patients with astrocytoma (two Grade III, eight Grade IV) using an 8‐channel receive coil at 3T. Lactate, lipid, choline, creatine, and N‐acetyl aspartate (NAA) signals were measured in regions of tumor and contralateral white matter. Metabolites were quantified relative to unsuppressed water using LCModel fitting software.

Results:

The within‐patient coefficients of variation were ≈16% (tumor lactate), 6%–8% (tumor choline and contralateral choline, creatine, and NAA), and 22% (tumor lipid). As expected due to their low concentration in normal tissue, lactate and lipid were not reliably detected in white matter but were found at high levels in most tumors. NAA and creatine were lower in tumors than in normal white matter, and choline varied between above‐ and below‐normal values. No consistent short‐term variation in metabolite levels was observed, despite differences in the time elapsed since administration of contrast agent.

Conclusion:

MRS appears repeatable enough to provide longitudinal measures of metabolite content in tumors and contralateral tissue in the brain in vivo. J. Magn. Reson. Imaging 2012;36:468–475. ©2012 Wiley Periodicals, Inc.
Tumor size predicts survival in mucinous gastric carcinoma
Authors: Sung Chang Ohk , Lee Sun Mi , Choi Jong Sun , Kim Kyoung‐Mee , Choi Min‐Gew , Noh Jae Hyung , Sohn Tae Sung , Bae Jae Moon , Kim Woo Ho , Park Cheol‐Keun , Kim Sung
Published: April 2012

Background

Mucinous gastric carcinoma (MGC) is a distinct histologic subtype of gastric cancer. However, the prognostic significances of the current TNM staging system and histology in MGC have not been studied.

Methods

206 patients who underwent R0 resection for MGC were classified by tumor size (<3 cm as T1; ≥3–5 cm as T2; ≥5–9 cm as T3; and ≥9 cm as T4). Immunohistochemistry for EGFR and HER2 was also performed.

Results

Tumor sizes ranged from 1.2 to 21.0 cm (median 6.2 cm). Large tumor size (≥5 cm) was significantly associated with older patient age, deeper invasion depth, and more frequent lymph node metastasis (P < 0.05). Tumor size was a significant prognostic factor in both univariate (P < 0.001) and multivariate (P < 0.04) analyses. However, depth of invasion was not significant in multivariate analyses. A modified staging system based on tumor size predicted survival more accurately than did the conventional TNM staging system. We verified our results in an independent validation cohort of 123 MGC patients. Overexpression of either EGFR or HER2 was rare.

Conclusions

In MGCs, tumor size is an independent prognostic factor and a modified TNM system based on tumor size predicted survival accurately. J. Surg. Oncol. 2012; 106:757–764. © 2012 Wiley Periodicals, Inc.
Accuracy of pharmacy and coded‐diagnosis information in identifying tuberculosis in patients with rheumatoid arthritis
Authors: Fiske Christina T. , Griffin Marie R. , Mitchel Ed , Sterling Timothy R. , Grijalva Carlos G.
Published: April 2012

Purpose

Previous studies suggest that disease‐modifying anti‐rheumatic drugs (DMARDs) increase tuberculosis (TB) risk. The accuracy of pharmacy and coded‐diagnosis information to identify persons with TB is unclear.

Methods

Within a cohort of rheumatoid arthritis (RA) patients (2000–2005) enrolled in Tennessee Medicaid, we identified those with potential TB using International Classification of Diseases, Ninth Revision, Clinical Modification (ICD9‐CM) diagnosis codes and/or pharmacy claims. Using the Tennessee TB registry as the gold standard for identification of TB, we estimated the sensitivity, specificity, predictive values, and the respective 95% confidence intervals for each TB case‐ascertainment strategy.

Results

Ten of 18 094 RA patients had confirmed TB during 61 461 person‐years of follow‐up (16.3 per 100 000 person‐years). The sensitivity and positive predictive value (PPV) and respective 95% confidence intervals were low for confirmed TB based on ICD9‐CM codes alone (60.0% (26.2–87.8) and 1.3% (0.5–2.9)), pharmacy data alone (20% (2.5–55.6) and 4.1% (0.5–14.3)), and both (20% (2.5–55.6) and 25.0% (3.2–65.1)).

Conclusions

Algorithms that use administrative data alone to identify TB have a poor PPV that results in a high false positive rate of TB detection. Copyright © 2012 John Wiley & Sons, Ltd.