bluuebunny/crossref_metadata_2025 huggingface dataset:
A comparison of the chemical sinks of atmospheric organics in the gas and aqueous phase
Authors: Epstein S. A. , Nizkorodov S. A.
Published: April 2012

Abstract. Photochemical reactions represent the main pathway for the removal of non-methane volatile organic compounds (VOCs) in the atmosphere. VOCs may react with hydroxyl radical (OH), the most important atmospheric oxidant, or they can be photolyzed by actinic radiation. In the presence of clouds and fog, VOCs may partition into the aqueous phase where they can undergo aqueous photolysis and/or reaction with dissolved OH. The significance of direct aqueous photolysis is largely uncertain due to the lack of published absorption cross sections and photolysis quantum yields. In light of this, we strive to identify atmospherically relevant VOCs where removal by aqueous photolysis may be a significant sink. The relative importance of different photochemical sinks is assessed by calculating the ratios of the removal rates inside air parcels containing cloud and fog droplets. This relative approach provides useful information in spite of the limited aqueous photolysis data. Results of this work should help guide researchers in identifying molecules that are the most likely to undergo aqueous OH oxidation and photolysis. We find that out of the 27 atmospherically relevant species investigated, the removal of glyceraldehyde and pyruvic acid by aqueous photolysis is potentially an important sink. We also determine the relative magnitudes of these four chemical sinks for the set of relevant organic compounds.
Global simulations of nitrate and ammonium aerosols and their radiative effects
Authors: Xu L. , Penner J. E.
Published: April 2012

Abstract. We examine the formation of nitrate and ammonium on five types of externally mixed pre-existing aerosols using the hybrid dynamic method in a global chemistry transport model. The model developed here predicts a similar spatial pattern of total aerosol nitrate and ammonium to that of several pioneering studies, but separates the effects of nitrate and ammonium on pure sulfate, biomass burning, fossil fuel, dust and sea salt aerosols. Nitrate and ammonium boost the scattering efficiency of sulfate and organic matter but lower the extinction of sea salt particles since the hygroscopicity of a mixed nitrate-ammonium-sea salt particle is less than that of pure sea salt. The direct anthropogenic forcing of particulate nitrate and ammonium at the top of atmosphere (TOA) is estimated to be −0.12 W m−2. Nitrate, ammonium and nitric acid gas also affect aerosol activation and the reflectivity of clouds. The first aerosol indirect forcing by anthropogenic nitrate (gas plus aerosol) and ammonium is estimated to be −0.09 W m−2 at TOA, almost all of which is due to nitric acid gas (−0.08 W m−2).
Operational considerations to improve total ozone measurements with a Microtops II ozone monitor
Authors: Gómez-Amo J. L. , Estellés V. , di Sarra A. , Pedrós R. , Utrillas M. P. , Martínez- Lozano J. A. , González-Frias C. , Kyrö E. , Vilaplana J. M.
Published: April 2012

Abstract. A Microtops II "ozone monitor" with UV channels centered at 305.5, 312.5, and 320 nm has been used routinely in six experimental campaigns carried out in several geographic locations and seasons, covering latitudes from 35 to 68° N during the last ten years (2001–2011). The total ozone content is retrieved by Microtops II by using different combinations (Channel I, 305.5/312.5 nm; Channel II, 312.5/320 nm; and Channel III, 305.5/312.5/320 nm) of the signals at the three ultraviolet wavelengths. The long-term performance of the total ozone content determination has been studied taking into account the sensitivities to the calibration, airmass, temperature and aerosols. When a calibration was used and the airmass limit was fixed to 3, the root mean square deviations of the relative differences produced by Microtops II with respect to several Brewers are 0.9, 2, and 2% respectively for the Channel I, Channel II, and Channel III retrieval. The performance of the Microtops retrieval has been stable during the last ten years. Channel I represents the best option to determine the instantaneous total ozone content. Channels II and III values appear weakly sensitive to temperature, ozone content, and aerosols. Channel II is more stable than Channel I for airmasses larger than 2.6. The conclusions do not show any dependence on latitude and season.
A remarkable correlation between short period gravity waves and semiannual oscillation of the zonal wind in the equatorial mesopause region
Authors: Venkateswara Rao N. , Tsuda T. , Kawatani Y.
Published: April 2012

Abstract. The variability of zonal winds and the horizontal wind velocity variance of short period (20–120 min) gravity waves (GWs) in the equatorial mesopause region are studied using medium frequency (MF) radar observations from Pameungpeuk (7.4° S, 107.4° E) during 2004–2010. The zonal winds display a distinct semiannual oscillation (called mesospheric semiannual oscillation, MSAO), with westward winds during equinoxes and eastward winds during solstices. Furthermore, the westward winds during March equinox are larger during 2008 and 2009. The short period GW variance also shows a semiannual oscillation with enhanced activity during equinoxes. A good correlation is observed between the zonal winds and the short period GW variance from 2008–2010, with the winds being westward during the times of enhanced GW activity. Such a correlation, however, is less obvious during 2004–2006. The long period (10–20 h) GW variance, on the other hand, does not show such a correlation throughout the observation period.
Spatial variations of nitrogen trace gas emissions from tropical mountain forests in Nyungwe, Rwanda
Authors: Gharahi Ghehi N. , Werner C. , Cizungu Ntaboba L. , Mbonigaba Muhinda J. J. , Van Ranst E. , Butterbach-Bahl K. , Kiese R. , Boeckx P.
Published: April 2012

Abstract. Globally, tropical forest soils represent the second largest source of N2O and NO. However, there is still considerable uncertainty on the spatial variability and soil properties controlling N trace gas emission. Therefore, we carried out an incubation experiment with soils from 31 locations in the Nyungwe tropical mountain forest in southwestern Rwanda. All soils were incubated at three different moisture levels (50, 70 and 90 % water filled pore space (WFPS)) at 17 °C. Nitrous oxide emission varied between 4.5 and 400 μg N m−2 h−1, while NO emission varied from 6.6 to 265 μg N m−2 h−1. Mean N2O emission at different moisture levels was 46.5 ± 11.1 (50 %WFPS), 71.7 ± 11.5 (70 %WFPS) and 98.8 ± 16.4 (90 %WFPS) μg N m−2 h−1, while mean NO emission was 69.3 ± 9.3 (50 %WFPS), 47.1 ± 5.8 (70 %WFPS) and 36.1 ± 4.2 (90 %WFPS) μg N m−2 h−1. The latter suggests that climate (i.e. dry vs. wet season) controls N2O and NO emissions. Positive correlations with soil carbon and nitrogen indicate a biological control over N2O and NO production. But interestingly N2O and NO emissions also showed a positive correlation with free iron and a negative correlation with soil pH (only N2O). The latter suggest that chemo-denitrification might, at least for N2O, be an important production pathway. In conclusion improved understanding and process based modeling of N trace gas emission from tropical forests will benefit from spatially explicit trace gas emission estimates linked to basic soil property data and differentiating between biological and chemical pathways for N trace gas formation.
Isotope fractionation between dissolved and suspended particulate Fe in the oxic and anoxic water column of the Baltic Sea
Authors: Staubwasser M. , Schoenberg R. , von Blanckenburg F. , Krüger S. , Pohl C.
Published: April 2012

Abstract. Fe isotope ratios and concentrations of dissolved Fe (Fedis, < 0.45 μm) and of suspended particulate Fe (FeSPM) from a depth profile in the Eastern Gotland Basin, Baltic Sea, show a sharp gradient in δ56Fedis across the suboxic interface with δ56Fedis = −0.4 ‰ in the euxinic deep basin and δ56Fedis = +0.3 ‰ in the oxic upper water column. The isotopic gradient overlaps with a strong concentration gradient of Fedis, a concentration maximum in FeSPM and lower δ56FeSPM values than δ56Fedis. These features indicate preferential loss of light Fe isotopes into suspended iron-oxyhydroxides (FeIOH) during typical oxidative precipitation across the redox interface in the marine environment. The sign of the fractionation, Δ56FeFe_IOH–Fe(II)(aq) < 0 ‰, is in contrast to similar, mostly non-marine redox environments, where Δ56FeFe_IOH–Fe(II)(aq) > 0 ‰. The difference appears to be the result of isotope exchange dominated by reaction kinetics in the marine water column, rather than equilibrium fractionation generally inferred for oxidative Fe precipitation elsewhere. High residual δ56Fedis immediately above the suboxic interface and throughout the oxic water column suggest that any potential Fe export from reducing waters or sediments into the open water column is enriched in the heavy isotopes. Within the suboxic to euxinic deep basin the decreasing δ56FeSPM trend with depth and a generally low δ56Fedis are comparable to trends in marine anoxic sediment profiles indicative of microbial reductive Fe dissolution. This confirms supply of dissolved Fe to the euxinic water column mainly from reductive dissolution of settling particles.
Glacial-interglacial variability in ocean oxygen and phosphorus in a global biogeochemical model
Authors: Palastanga V. , Slomp C. P. , Heinze C.
Published: April 2012

Abstract. The importance of particulate organic carbon and phosphorus (P) delivered from shelves on open ocean productivity, oxygen, and reactive P burial during glacial times has been assessed using a biogeochemical ocean model of the carbon (C), P and iron cycles. The model shows that in simulations of the Last Glacial Maximum (LGM) without any inputs of terrigenous material from shelves there is a moderate increase in productivity (+5 %) and mean deep water oxygen (+29 %) relative to the preindustrial simulation. However, when the input of terrigenous particulate organic C and P is considered as an additional forcing in the LGM simulation, ocean productivity increases by 46 %, mean deep water oxygen concentration decreases by 20 %, and the global rate of reactive P burial is 3 times over the preindustrial value. The associated pattern of negative oxygen anomalies at 1000 m induces a deepening of the Atlantic and Indian Ocean oxygen minimum (OMZ), while in the Pacific Ocean the OMZ is shifted to the eastern basin north of the Equator relative to preindustrial times. In addition, negative trends in oxygen extend globally below 2000 m depth, though their magnitude is rather weak, and in particular bottom waters remain above suboxic levels. Changes in dust deposition can be responsible for positive trends in reactive P burial as simulated at the LGM in open ocean regions, notably over the Southwest Atlantic and Northwest Pacific; on the other hand, inputs of terrigenous material from shelves cause an increase in P burial over the continental slope and rise regions which accounts for 47 % of the total reactive P burial change. Although the glacial-interglacial trends in P burial in our model compare well with the available observations, this study highlights the need of much more core records of C and P in open ocean settings.
Hydrogeological characterisation of a glacially affected barrier island – the North Frisian Island of Föhr
Authors: Burschil T. , Scheer W. , Kirsch R. , Wiederhold H.
Published: April 2012

Abstract. We present the application of geophysical investigations to characterise and improve the geological/hydrogeological model through the estimation of petrophysical parameters for groundwater modelling. Seismic reflection and airborne electromagnetic surveys in combination with borehole information enhance the 3-D geological model and allow a petrophysical interpretation of the subsurface. The North Sea Island of Föhr has a very complex underground structure what was already known from boreholes. The local waterworks use a freshwater body embedded in saline groundwater. Several glaciations disordered the Youngest Tertiary and Quaternary sediments by glaciotectonic thrust-faulting as well as incision and refill of glacial valleys. Both underground structures have a strong impact on the distribution of freshwater bearing aquifers. An initial hydrogeological model of Föhr was built from borehole data alone and was restricted to the southern part of the island where in the sandy areas of the Geest a large freshwater body was formed. We improved the geological/hydrogeological model by adding data from different geophysical methods, e.g. airborne electromagnetics (EM) for mapping the resistivity of the entire island, seismic reflections for detailed cross sections in the groundwater catchment area, and geophysical borehole logging for calibration of these measurements. An integrated evaluation of the results from the different geophysical methods yields reliable data. To determinate petrophysical parameter about 18 borehole logs, more than 75 m deep, and nearby airborne EM inversion models were analyzed concerning resistivity. We establish an empirical relation between measured resistivity and hydraulic conductivity for the specific area – the North Sea island of Föhr. Five boreholes concerning seismic interval velocities discriminate sand and till. The interpretation of these data was the basis for building the geological/hydrogeological 3-D model. We fitted the relevant model layers to all geophysical and geological data and created a consistent 3-D model. This model is the fundament for groundwater simulations considering forecasted changes in precipitation and sea level rise due to climate change.
Usefulness of four hydrological models in simulating high-resolution discharge dynamics of a catchment adjacent to a road
Authors: Kalantari Z. , Jansson P.-E. , Stolte J. , Folkeson L. , French H. K. , Sassner M.
Published: April 2012

Abstract. Four hydrological models (LISEM, MIKE SHE, CoupModel and HBV) were compared with respect to their capability to predict peak flow in a small catchment upstream of a road in SE Norway on an hourly basis. All four models were calibrated using hourly observed streamflow. Simulated and observed discharge generated during three types of hydrological situations characteristic of winter/spring conditions causing overland flow were considered: snowmelt, partially frozen soil and heavy rain events. Using parameter sets optimised for winter/spring conditions, flows simulated by HBV coupled with CoupModel were comparable to measured discharge from the catchment in corresponding periods. However, this combination was best when all the parameters were calibrated in HBV. For ungauged basins with no real-time monitoring of discharge and when the spatial distribution is important, MIKE SHE may be more suitable than the other models, but the lack of detailed input data and the uncertainty in physical parameters should be considered. LISEM is potentially capable of calculating runoff from small catchments during winter/spring but requires better description of snowmelt, infiltration into frozen layers and tile drainage. From a practical road maintenance perspective, the usefulness and accuracy of a model depends on its ability to represent site-specific processes, data availability and calibration requirements.
Role of climate forecasts and initial land-surface conditions in developing operational streamflow and soil moisture forecasts in a rainfall-runoff regime: skill assessment
Authors: Sinha T. , Sankarasubramanian A.
Published: April 2012

Abstract. Skillful seasonal streamflow forecasts obtained from climate and land surface conditions could significantly improve water and energy management. Since climate forecasts are updated on monthly basis, we evaluate the potential in developing operational monthly streamflow forecasts on a continuous basis throughout the year. Further, basins in the rainfall-runoff regime critically depend on the forecasted precipitation in the upcoming months as opposed to snowmelt regimes where initial hydrological conditions (IHC) play a critical role. The goal of this study is to quantify the role of monthly updated precipitation forecasts and IHC in forecasting 6-month lead monthly streamflow for a rainfall-runoff mechanism dominated basin – Apalachicola River at Chattahoochee, FL. The Variable Infiltration Capacity (VIC) land surface model is implemented with two forcings: (a) monthly updated precipitation forecasts from ECHAM4.5 Atmospheric General Circulation Model (AGCM) forced with sea surface temperature forecasts and (b) daily climatological ensemble. The difference in skill between the above two quantifies the improvements that could be attainable using the AGCM forecasts. Monthly retrospective streamflow forecasts are developed from 1981 to 2010 and streamflow forecasts estimated from the VIC model are also compared with those predicted by using the principal component regression (PCR) model. Mean square error (MSE) in predicting monthly streamflow using the above VIC model are compared with the MSE of streamflow climatology under ENSO conditions as well as under normal years. Results indicate that VIC forecasts, at 1–2 month lead time, obtained using ECHAM4.5 are significantly better than VIC forecasts obtained using climatological ensemble over all the seasons except forecasts issued in fall and the PCR models perform better during the fall months. Over longer lead times (3–6 months), VIC forecasts derived using ECHAM4.5 forcings alone performed better compared to the MSE of streamflow climatology during winter and spring seasons. During ENSO years, streamflow forecasts exhibit better skill even up to six month lead time. Comparison of the seasonal soil moisture forecasts developed using ECHAM4.5 forcings with seasonal streamflow also show significant skill at 1–3 month lead time over the all four seasons.
Plan to Restore the Vote: Ron Paul and the Third-Party Voting Dilemma
Authors: Anzur Jonathan C.
Published: April 2012

Texas Congressman and Republican presidential candidate Ron Paul has been a figure in American politics for more than 40 years. While Paul has commanded a dedicated support base composed of both liberals and conservatives, he remains well behind in the 2012 Republican primary race. This article examines the hypothetical case of a Ron Paul third-party presidential run, and the dilemma that voters face between voting conscientiously for Paul and voting strategically for the most electable and ideologically similar candidate.
The morphology of Ganoderma species with a laccate surface
Authors: Torres-Torres Mabel Gisela , Guzmán-Dávalos Laura
Published: April 2012

A discussion on the importance of morphological features in the taxonomy of Ganoderma subg. Ganoderma is presented. More than 500 specimens of 37 species, including 33 types, were checked: G. argillaceum, G. atkinsonii, G. boninense, G. capense,
G. chonoides, G. colossus, G. concinnum, G. corrugatum, G. curtisii, G. dorsale, G. elegantum, G. longistipitatum, G. mexicanum, G. multicornum, G. multiplicatum, G. nevadense, G. nitidum, G. oerstedii, G.
orbiforme, G. oregonense, G. parvulum, G. perturbatum, G. perzonatum, G. praelongum, G. pulverulentum, G. ravenelii, G. resinaceum, G. sequoiae, G. sessile, G. sessiliforme, G. simulans, G. stipitatum,
G. subfornicatum, G. subincrustatum, G. vivianimercedianum, G. weberianum, and G. zonatum. Color of the context, resinous deposits, structure of the basidiospores, and protuberances of the pileipellis cells are among the most important features for characterization
of the species.
Two new Heteroconium species and two other forest microfungi newly recorded from China
Authors: Ren Shou-Cai , Ma Jian , Zhang Xiu-Guo
Published: April 2012

Two new species, Heteroconium annesleae on decaying branches of Anneslea hainanensis and H. neolitseae on decaying branches of Neolitsea obtusifolia, are described, illustrated, and compared with closely related taxa. Illustrations are also provided of two
other anamorphic fungi, Xenoheteroconium bicolor and Craspedodidymum fimbriatum, which are recorded for the first time from China.
A new hairy species of Leptogium (Collemataceae) from China
Authors: Liu Hua-Jie , Guan Shuai
Published: April 2012

This paper describes Leptogium weii sp. nov., a new hairy species from Sichuan, southwestern China. Leptogium weii has dense white tomentum on apothecial stalks and thalline margins. It closely resembles L. burnetiae in external morphology but differs in having
globose isidia on the upper surface and dense tomentum on the apothecial stalk and thalline margin. A key is given to hairy species with tomentose apothecia.
Activating Death Receptor DR5 as a Therapeutic Strategy for Rhabdomyosarcoma
Authors: Kang Zhigang , Sun Shi-Yong , Cao Liang
Published: April 2012

Rhabdomyosarcoma (RMS) is the most common soft tissue sarcoma in children. It is believed to arise from skeletal muscle progenitors, preserving the expression of genes critical for embryonic myogenic development such asMYOD1andmyogenin. RMS is classified as embryonal, which is more common in younger children, or alveolar, which is more prevalent in elder children and adults. Despite aggressive management including surgery, radiation, and chemotherapy, the outcome for children with metastatic RMS is dismal, and the prognosis has remained unchanged for decades. Apoptosis is a highly regulated process critical for embryonic development and tissue and organ homeostasis. Like other types of cancers, RMS develops by evading intrinsic apoptosis via mutations in thep53tumor suppressor gene. However, the ability to induce apoptosis via the death receptor-dependent extrinsic pathway remains largely intact in tumors withp53mutations. This paper focuses on activating extrinsic apoptosis as a therapeutic strategy for RMS by targeting the death receptor DR5 with a recombinant TRAIL ligand or agonistic antibodies directed against DR5.
Endoscope-Assisted Tonsillotomy (Partial Intracapsular Tonsillectomy): How We Do It
Authors: Uzomefuna Vincent , Glynn Fergal
Published: April 2012

Objective. To describe our technique of performing tonsillotomy that increases visibility by providing a better view of the tonsils and related structures through the use of a 30-degree scope. Method. Patients had tonsillotomy with microdebrider with the aid of a 30-degree endoscope for both visualization and on-screen projection and magnification. Result. The endoscope-assisted technique provides a more detailed exposure of pharyngeal structures and their relationships with the tonsils. It is easier to clearly visualize the upper and lower poles. The magnification with the endoscope makes it easier to appreciate anatomic details and identify/deal selectively with minute bleeding points. Conclusion. The use of 30-degree endoscope in tonsillotomy provides better visualization of the upper and lower tonsil poles and may make the procedure easier for the surgeon and safer for the patient.
Selective Palladium‐Catalyzed Suzuki–Miyaura Reactions of Polyhalogenated Heteroarenes
Authors: Rossi Renzo , Bellina Fabio , Lessi Marco
Published: April 2012

The palladium‐catalyzed Suzuki–Miyaura reaction of multiply halogenated, electron‐rich and electron‐deficient heteroarenes is one of the most reliable and environmentally friendly tools for installing a wide range of non‐functionalized and functionalized carbon substituents onto heteroaromatic systems with exquisite chemo‐ and site‐selectivity. For substrates with different halogen groups the chemoselectivity of the Suzuki–Miyaura reactions has been found to be dependent on the reactivity difference between the halogens. However, the hardest achievement of selectivity in Suzuki–Miyaura monocouplings involving polyhalogenated heteroarenes with identical halogen atoms has been shown to be dominated by steric and electronic effects and the presence of directing groups at positions neighbouring the reaction sites. Moreover, in the case of symmetrically substituted dihaloheteroarenes with identical halogen atoms, highly selective monocoupling reactions have often been achieved only after a careful optimization of reaction parameters including the catalyst precursor, base, solvent, and the molar ratio between electrophile and organoboron reagent. This critical review with 341 references covers developments on the chemo‐ and site‐selective Suzuki–Miyaura monocoupling reactions of polyhalogenated heteroarenes with different or identical halogen atoms. It also includes the synthesis of polysubstituted heteroarenes, not easily accessible by other means, via consecutive monocoupling reactions and/or a more synthetically valuable approach involving one‐pot polycoupling reactions.
Novel use of an Amplatzer Vascular Occluder II to close an acquired fistula between a reconstructed aortic arch and the left atrial appendage in a patient with hypoplastic left heart syndrome
Authors: Bielefeld Kyle J. , Seib Paul M. , Fontenot Eudice E.
Published: April 2012

An 8‐month‐old female with hypoplastic left heart syndrome had undergone bidirectional cavopulmonary anastomosis at the age of 4.5 months and presented with a new continuous flow murmur on routine follow‐up. Diagnostic catheterization demonstrated a fistula between the left atrial appendage and the neo‐aortic arch. The fistula was sealed with an Amplatzer Vascular Occluder II device without complications. © 2012 Wiley Periodicals, Inc.
A Strategy for Dramatically Enhancing the Selectivity of Molecules Showing Aggregation‐Induced Emission towards Biomacromolecules with the Aid of Graphene Oxide
Authors: Xu Xiujuan , Li Jijun , Li Qianqian , Huang Jing , Dong Yongqiang , Hong Yuning , Yan Jiawei , Qin Jingui , Li Zhen , Tang Ben Zhong
Published: April 2012

By intelligently utilizing the different interacting strengths between different moieties according to the displacement method, general biosensors with aggregation‐induced emission (AIE) characteristics for biomacromolecules without selectivity were converted to excellent, highly selective probes for one specific biomacromolecule with the aid of graphene oxide (GO) in an aqueous medium. Importantly, thanks to the different interactions between the AIE molecule and biomacromolecules, just by simply changing the AIE molecule the sensing system could detect different types of biomacromolecules, thereby providing a new approach to the development of AIE‐based sensors with high selectivity and sensitivity. More specifically, the complex of A2HPS⋅HCl—a derivative of hexaphenylsilone (HPS) functionalized by two amino (A2) groups (N(CH2CH3)3)—and GO only gives an “off–on” response to DNA, with a detection limit of 2.3 μg mL−1 toward DNA‐CT (calf thymus); interestingly, the complex of TPE‐N2C4 (1,2‐bis{4‐[4‐(N,N,N‐triethylammonium)butoxy]phenyl}‐1,2‐diphenylethene dibromide) and GO could only detect the presence of bovine serum albumin (BSA), whereas other biomacromolecules, including DNA, RNA, and even other proteins have very little influence.
Tautomeric Switching and Metal‐Cation Sensing of Ligand‐Equipped 4‐Hydroxy‐/4‐oxo‐1,4‐dihydroquinolines
Authors: Todorov Aleksandar R. , Nieger Martin , Helaja Juho
Published: April 2012

Novel 4‐hydroxyquinoline (4HQ) based tautomeric switches are reported. 4HQs equipped with coordinative side arms (8‐arylimino and 3‐piperidin‐1‐ylmethyl groups) were synthesized to access O‐ or N‐selective chelation of Zn2+ and Cd2+ ions by 4HQ. In the case of the monodentate arylimino group, O chelation of metal ions induces concomitant switching of phenol tautomer to the keto form in nonpolar or aprotic media. This change is accompanied by selective and highly sensitive fluorometric sensing of Zn2+ ions. In the case of the bidentate 8‐(quinolin‐8‐ylimino)methyl side arm, NMR studies in CD3OD indicated that both Cd2+ and Zn2+ ions afford N chelation for 4HQ, coexisting with tautomeric switching from quinolin‐4(1H)‐one to quinolin‐4‐olate. In corroboration, UV/Vis‐monitored metal‐ion titrations in toluene and methanol implied similar structural changes. Additionally, fluorescence measurements indicated that the metal‐triggered tautomeric switching is associated with compound signaling properties. The results are supported by DFT calculations at the B3LYP 6‐31G* level. Several X‐ray structures of metal‐free and metal‐chelating 4HQ are presented to support the solution studies.
Stereoselective Synthesis of α‐ and β‐Glycofuranosyl Amides by Traceless Ligation of Glycofuranosyl Azides
Authors: Nisic Filippo , Speciale Gaetano , Bernardi Anna
Published: April 2012

A highly stereoselective synthesis of α‐ or β‐glycofuranosyl amides based on the traceless Staudinger ligation of glycofuranosyl azides of the galacto, ribo, and arabino series with 2‐diphenylphosphanyl‐phenyl esters has been developed. Both α‐ and β‐isomers can be obtained with excellent selectivity from a common, easily available precursor. The process does not depend on the anomeric configuration of the starting azide but appears to be controlled by the C2 configuration and by the protection/deprotection state of the substrates. A mechanistic interpretation of the results, supported by 31P NMR experiments, is offered and merged with our previous mechanistic analysis of pyranosyl azide ligation reactions.
Patterns of failure in patients with early onset (synchronous) resectable liver metastases from rectal cancer
Authors: Butte Jean M. , Gonen Mithat , Ding Peirong , Goodman Karyn A. , Allen Peter J. , Nash Garrett M. , Guillem Jose , Paty Philip B. , Saltz Leonard B. , Kemeny Nancy E. , DeMatteo Ronald P. , Fong Yuman , Jarnagin William R. , Weiser Martin R. , D'Angelica Michael I.
Published: April 2012

BACKGROUND:

The optimal combination of available therapies for patients with resectable synchronous liver metastases from rectal cancer (SLMRC) is unknown, and the pattern of recurrence after resection has been poorly investigated. In this study, the authors examined recurrence patterns and survival after resection of SLMRC.

METHODS:

Consecutive patients with SLMRC (disease‐free interval, ≤12 months) who underwent complete resection of the rectal primary and liver metastases between 1990 and 2008 were identified from a prospective database. Demographics, tumor‐related variables, and treatment‐related variables were correlated with recurrence patterns. Competing risk analysis was used to determine the risk of pelvic and extrapelvic recurrence.

RESULTS:

In total, 185 patients underwent complete resection of rectal primary and liver metastases. One hundred eighty patients (97%) received chemotherapy during their treatment course, and 91 patients (49%) received pelvic radiation therapy either before (N = 65; 71.4%), or after (N = 26; 28.6%) rectal resection. The 5‐year disease‐specific survival rate was 51% for the entire cohort with a median follow‐up of 44 months for survivors. One hundred thirty patients (70%) developed a recurrence: Eighteen patients (10%) had recurrences in the pelvis in combination with other sites, and 7 of these (4%) had an isolated pelvic recurrence. Recurrence pattern did not correlate with survival. Competing risk analysis demonstrated that the likelihood of a pelvic recurrence was significantly lower than that of an extrapelvic recurrence (P < .001).

CONCLUSIONS:

Of the patients with SLMRC who developed recurrent disease, systemic sites were overwhelmingly more common than pelvic recurrences. The current results indicated that the selective exclusion of radiotherapy may be considered in patients who are diagnosed with simultaneous disease. Cancer 2012. © 2012 American Cancer Society.
Postradiation sarcoma: Morphological findings on fine‐needle aspiration with clinical correlation
Authors: Olson Matthew T. , Wakely Paul E. , Weber Kristy , Siddiqui Momin T. , Ali Syed Z.
Published: April 2012

BACKGROUND:

The current study was conducted to describe the clinical features and presentation, cytomorphological characteristics with histological correlation, and prognosis of patients who undergo fine‐needle aspiration (FNA) for postradiation sarcoma (PRS).

METHODS:

A retrospective review was performed of 13 individual patients who were pooled from the FNA services of 3 academic institutions between 2001 and 2012. Cases were reviewed for the primary tumor, radiation history, latency period, and other distinguishing clinical features. The frequency of the various cytological preparations as well as the use of immunohistochemistry (IHC) on this material were reviewed. The cytopathology diagnosis was compared with the resection diagnosis, and the survival time was reviewed.

RESULTS:

The median age of the patients was 61 years (range, 35 years‐94 years) and no significant gender predilection was noted. The median latency period was 11 years (range, 5 years to > 50 years). Patients generally presented with large tumors (median, 8 cm [range, 3 cm‐12 cm]), and the median survival was 14 months (range, 6 months‐46 months). Nine of 13 patients died of their disease and 1 was lost to follow‐up. The tumors were morphologically heterogeneous. IHC played an important role in excluding other diagnoses in those cases in which sufficient material was available.

CONCLUSIONS:

PRS is a morphologically heterogeneous entity that can be diagnosed by FNA. It is a diagnosis of exclusion that requires a history of therapeutic radiation and often requires IHC to rule out locally recurrent malignancy. Cancer (Cancer Cytopathol) 2012. © 2012 American Cancer Society.
Surface Electronic Structure of [XMIm]Cl Probed by Surface‐Sensitive Spectroscopy
Authors: Ulbrich Angela , Reinmöller Markus , Beenken Wichard J. D. , Krischok Stefan
Published: April 2012

We apply electron spectroscopy methods with different surface sensitivities to elucidate the DOS of the surface and the near‐surface region of [XMIm]Cl (X=octyl, hexyl, butyl, and ethyl alkyl chain) ionic liquids. Using metastable induced electron spectroscopy (MIES) we are able to detect the density of states in front of the outermost surface, whereas ultraviolet and X‐ray photoelectron spectroscopy (UPS and XPS) measurements provide lower surface sensitivity. The assignment of certain structures in the valence band spectra to particular atoms/functional groups of the ionic liquid based on DFT calculations and the reconstruction of PES spectra enables us to obtain information on the dominating groups at the surface, or in other words, on the molecular/ionic arrangement and orientation at the surface. From angular resolved XPS it is concluded that the alkyl chains dominate at the outermost surface. In agreement with this a decreasing chlorine signal is observed in the UPS spectra for ionic liquids with increasing alkyl chain length. The analysis of the MIES data shows that in case of [OMIm]Cl—in contrast to UPS and XPS—no Cl‐induced features are visible in the MIES spectra at all and that the MIES spectra are dominated by the [OMIm]+ alkyl chain.
Enhancing the Efficiency of SOFC‐Based Auxiliary Power Units by Intermediate Methanation
Authors: Göll S. , Samsun R. C. , Peters R.
Published: April 2012

Fuel‐cell‐based auxiliary power units benefit from the high power density and fuel flexibility of solid oxide fuel cells (SOFCs), facilitating straightforward onboard fuel processing of diesel or jet fuel. The preferred method of producing the fuel gas is autothermal reforming, which to date has shown the best practical applicability. However, the resulting reformate is poor in methane, so that cell cooling is not supported by internal methane steam reforming. Accordingly, large flow rates of excess air are required to cool the stack. Hence, the power demand of the cathode air blower significantly limits the net electrical power output of the system and large cathode flow channels are required. The present work examines attempts to further increase the system efficiency in middle‐distillate‐fueled SOFC systems by decreasing the cathode air flow rates. The proposed concept is generally based on inducing endothermic methane steam reforming (MSR) inside the cells by augmenting the methane content in an upstream methanation step. Methanation, however, can only yield significant methane production rates if the reaction temperature is limited. Therefore, four process layouts are presented that include different cooling measures. Based on these setups, the general feasibility and the benefit of intermediate methanation are demonstrated.
State regulation: Interstate compacts a policy option to enhance transmission line siting
Authors: deGolian Crady
Published: April 2012

Siting electric transmission lines across state borders has long been a challenge for the states, the federal government, and utility transmission companies. Too often, the diverse interests of various stakeholders, combined with the absence of a mechanism capable of bringing different entities together, makes siting interstate electric transmission lines a difficult proposition. The multiyear application review process and separate evaluations by multiple jurisdictions constitutes a growing burden for transmission companies and frustrates state and federal policymakers seeking to move renewable energy and lower‐cost electricity to markets.
Preparedness: Preparedness standards can have positive effect on utilities
Authors: Byrne Don
Published: April 2012

The terrorist attacks of September 11, 2001, were an enormous call to action. Only two months later, the Patriot Act was passed, and by the following Thanksgiving, 22 federal agencies were consolidated into the Department of Homeland Security (DHS), making it the third‐largest Cabinet agency behind the Department of Defense and the Department of Veterans Affairs.
Palaeogeographic Changes at Lake Chokrak on the Kerch Peninsula, Ukraine, during the Mid‐ and Late‐Holocene
Authors: Kelterbaum Daniel , Brückner Helmut , Dikarev Vasiliy , Gerhard Stefanie , Pint Anna , Porotov Alexey , Zin'ko Victor
Published: April 2012

This project has reconstructed the palaeogeographic and environmental evolution of Lake Chokrak on the Kerch Peninsula, Ukraine, during the mid‐ and late‐Holocene. This record has been evaluated in association with a regional archaeological data set to explore human–environment interactions over this period. The results show major changes in the palaeogeographic setting of Lake Chokrak since the 3rd millennium B.C., when the postglacial marine transgression had started to fill the study area. Microfaunal analyses reveal the long persistence of an open marine embayment that only became separated from the Sea of Azov when a sand barrier developed during the late 2nd millennium B.C. When colonizing the Black Sea region after the 8th century B.C., the Greek settlers erected a fortification with a small settlement on a promontory that was by then a peninsula‐like headland extending into the lake. The colonists abandoned their settlement at the end of the 1st millennium B.C. when the depth of the surrounding lake decreased from 1.5 m to less than 1 m. Today, Lake Chokrak dries up completely during summer. A detailed relative sea level (RSL) curve for the northern coast of Kerch has been established. Sea level reached its highest position at the present day. Since the 3rd millennium B.C., sea level continuously rose, without any of the previously postulated regression/transgression cycles. The RSL curve indicates differential subsidence rates within short distances in relatively stable areas, exceeding 40 cm per 1000 years. © 2012 Wiley Periodicals, Inc.
THE DYNAMICS OF INCOME‐RELATED HEALTH INEQUALITY AMONG AMERICAN CHILDREN
Authors: Chatterji Pinka , Lahiri Kajal , Song Jingya
Published: April 2012

We estimate and decompose income‐related inequality in child health in the USA and analyze its dynamics using the recently introduced health mobility index. Data come from the 1997, 2002, and 2007 waves of the Child Development Supplement of the Panel Study of Income Dynamics. The findings show that income‐related child health inequality remains stable as children grow up and enter adolescence. The main factor underlying income‐related child health inequality is income itself, although other factors, such as maternal education, also play a role. Decomposition of income‐related health mobility indicates that health changes over time are more favorable to children with lower initial family incomes versus children with higher initial family incomes. However, offsetting this effect, our findings also suggest that changes in income ranking over time are positively related to children's subsequent health status. Copyright © 2012 John Wiley & Sons, Ltd.
Does state budget pressure matter for uncompensated care spending in hospitals? Findings from Texas and California
Authors: Chang Jongwha , Patel Isha , Suh Won S. , Lin Hsien‐Chang , Kim SunJung , Balkrishnan Rajesh
Published: April 2012

Objective

This study examined the impact of state budget cuts on uncompensated care at general acute care hospital organizations. This study capitalized on the variations in the states of Texas and California to form a natural experiment testing the joint impact of budget cut status on uncompensated care costs, as well as specific charity care costs and bad debt expenses from indigent patients.

Methodology

Budget cuts in the state of Texas occurred in the year 2004. Information was obtained from the Texas Department of Health and the California Department of Health Services regarding financial characteristics of hospitals and from the American Hospital Directory annual survey regarding organizational characteristics of hospitals. We created three dependent variables: RUC (the ratio of total uncompensated care costs to gross patient revenue), RCC (the ratio of charity care to total patient revenue) and RBD (the ratio of bad debt expenses to gross patient revenue). Using a two‐period panel data set and individual hospital fixed effects, we captured hospital uncompensated care spending that could also have influenced budget cut status. Additionally, the impact of the state budget cut status on hospitals' uncompensated care spending, charity care spending and bad debt expenses was also estimated using the similar methodology.

Population studied

In this study, we included 416 (in Texas) and 352 (in California) public, not‐for‐profit (NFP) and for‐profit (FP) hospitals that completed the annual survey during the study period 2002–2005.

Findings

For the state of Texas, results from the fixed effect model confirmed that the year 2005 was directly related to increased RUC and RCC. The coefficients of 2005 were significantly and positively associated with RUC (0.43, p < 0.05) and RCC (0.29, p < 0.05). These results supported the findings that the RUC and the RCC would be more positively associated with 2005 than any other year, with other things being equal. However, for the state of California, even though the coefficient of 2005 was significant and positively associated with RCC (0.31, p < 0.05), the coefficient of uncompensated care spending was not statistically significant for 2005.

Conclusion

The healthcare industry is characterized by increased regulation, a growing number of uninsured patients, increasingly stringent reimbursement and competitive practices among hospitals and other providers. Federal and state healthcare agencies are restricting the criteria for eligibility for outlier payments and uncompensated care provisions. Tax exempt status of many NFP hospitals is being examined and tied to specific performances, particularly the provision of uncompensated care. This study provides evidence of the impact of budget cut pressure on uncompensated care provided in Texas general acute care hospitals. Copyright © 2012 John Wiley & Sons, Ltd.
In vitro and in vivo study of calcium polyphosphate fiber/calcium phosphate cement/micromorselized bone composite for bone defect repair
Authors: Zhou Lei , Hu Chun J. , Xu Gong P. , Yan Jing L.
Published: April 2012

The aim of this study was to develop a superior bone engineering material for repair of bone defects. A composite of calcium polyphosphate fiber (CPPF)/calcium phosphate cement (CPC)/micromorselized bone was prepared. A scanning electron microscope was used to observe the structure of the composite and measure its porosity. Seventy‐two pieces of the material were placed in phosphate buffer solution and changes in pH were measured over time, and compressive strength was also measured. In vivo experiments were carried out on 72 rabbits divided into six groups: bone implantation with CPPF/CPC/micromorselized bone, CPC/micromorselized bone, micromorselized bone, CPPF/CPC, CPC, respectively; and no implantation (control). The implants were assessed with X‐ray film and histologically, and bone density and biomechanical strength were measured. The study period was 12 weeks. The addition of CPPF increased apertures of the composite. The bone defects in the CPPF/CPC/micromorselized group compared with the other groups had significantly higher radiographic grading and significantly greater bone density (p < 0.05) and biomechanical strength (p < 0.05). The new composite improves the speed and quality of bone formation. The addition of CPPF improved the mechanical properties of the scaffold material and created higher porosity. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater: 100B:1190–1197 2012.
Comparison of the FeO2+ and FeS2+ complexes in the cyanide and isocyanide ligand environment for methane hydroxylation
Authors: Tang Hao , Li Zhuo , Yang Yu‐Hong , Zhao Ying , Wan Su‐Qin , Liu Hui‐Ling , Huang Xu‐Ri
Published: April 2012

A general comparison of fundamental distinctions between the FeO2+ and FeS2+ complexes in an identical cyanide or isocyanide ligand environment for methane hydroxylation has been probed computationally in this work in a series of hypothetical [FeIV(X)(CN)5]3−, [FeIV(X)(NC)5]3−, (X = O, S) complexes. We have detailed an analysis of the geometric and electronic structures using density functional theory calculations. In addition, their σ‐ and π‐mechanisms in CH bond activation process have been described with the aid of the schematic molecular orbital diagram. From our theoretical results, it is shown that (a) the iron(IV)‐sulfido complex apparently is able to hydroxylate CH bond of methane as good as the iron(IV)‐oxo species, (b) the OCN, SCN complexes have an inherent preference for the low‐spin state, while for the case of ONC and SNC in which S = 1 and S = 2 states are relatively close in energy, (c) each of the d block electron orbital plays an important role, which is not just spectator electron, and (d) in comparison to the cyanide and isocyanide ligand environment, we can see that the FeS2+ species prefer the cyanide ligand environment, while the FeO2+ species favor the isocyanide ligand environment. In addition, a remarkably good correlation of the σ‐/π‐mechanism for hydrogen abstraction from methane with the gap between the Fe‐dz2 (α) and CH (α) pair as well as the Fe‐dxz/yz (β) and CH (β) pair has been found. © 2012 Wiley Periodicals, Inc.
Cooperative action of JNK and AKT/mTOR in 1‐methyl‐4‐phenylpyridinium‐induced autophagy of neuronal PC12 cells
Authors: Rodríguez‐Blanco Jezabel , Martín Vanesa , García‐Santos Guillermo , Herrera Federico , Casado‐Zapico Sara , Antolín Isaac , Rodriguez Carmen
Published: April 2012

Parkinson's disease has been widely related to both apoptosis and oxidative stress. Many publications relate the loss of mitochondrial potential to an apoptosis‐mediated cell death in different in vivo and in vitro models of this pathology. The present study used the dopaminegic specific neurotoxin 1‐methyl‐4‐phenylpyridinium (MPP+) on neuron‐like PC12 cells, which is a well‐accepted model of Parkinson's disease. Results showed an early increase in oxidants, which drives the modulation of c‐Jun N‐terminal kinase (JNK) and AKT/mammalian target of rapamycin (mTOR) pathways, mimicking peroxide treatment. However, the cell death found in neuronal PC12 cells treated with MPP+ was not a caspase‐associated apoptosis. Electron microscopic images illustrated autophagic cell death, which was confirmed by a Beclin‐1 and ATG expression increase, accumulation of acidic vesicles, and rescue by an autophagy inhibitor. In conclusion, the boost in oxidants from MPP+ treatment in neuronal PC12 is modulating both survival (AKT/mTOR) and death (JNK) pathways, which are the perpetrators of an autophagic cell death. © 2012 Wiley Periodicals, Inc.