bluuebunny/crossref_metadata_2025 huggingface dataset:
Bromide Complexation by the EuIII Lanthanide Cation in Dry and Humid Ionic Liquids: A Molecular Dynamics PMF Study
Authors: Chaumont Alain , Wipff Georges
Published: May 2012

We report a molecular dynamics study on the EuBrn3‐n complexes (n=0 to 6) formed upon complexation of Br− by Eu3+ in the [BMI][PF6], [BMI][Tf2N] and [MeBu3N][Tf2N] ionic liquids (ILs), to compare the effect of the IL anion (PF6− versus Tf2N−), the IL cation (BMI+ versus MeBu3N+) and the “IL humidity” on their solvation and stability. In “dry” solutions all complexes remain stable and the first coordination shell of Eu3+ is purely anionic (Br− and IL anions), surrounded by IL cations (BMI+ or MeBu3N+ ions). Long range “onion type” solvation features (up to 20 Å from Eu3+), with alternating cation‐rich and anion‐rich solvent shells, are observed around the different complexes. The comparison of gas phase‐optimized structures of EuBrn3‐n complexes (that are unstable for n=5 and 6) with those observed in solution points to the importance of solvation forces on the nature of the complex, with a higher stabilization by imidazolium‐ than by ammonium‐based dry ILs. Adding water to the IL has different effects, depending on the IL. In the highly hygroscopic [BMI][PF6] IL, Br− ligands are displaced by water, to finally form Eu(H2O)93+. In the less “humid” [BMI][Tf2N], the EuBrn3‐n complexes do not dissociate and coordinate at most 1–2 H2O molecules. We also calculated the free‐energy profiles (Potential of Mean Force calculations) for the stepwise complexation of Br−, and found significant solvent effects. EuBr63− is predicted to form in both [BMI][PF6] and [BMI][Tf2N], but not in [MeBu3N][Tf2N], mainly due to weaker interactions with the cationic solvation shell. First steps are found to be more exergonic in the PF6−‐ than in the Tf2N−‐based IL. Molecular dynamics (MD) comparisons between ILs and classical solvents (acetonitrile and water) are also reported, affording good agreement with the experimental observations of Br− complexation by trivalent lanthanides in these classical solvents.
Ion‐Specific Aggregation of Hydrophobic Particles
Authors: López‐León Teresa , Ortega‐Vinuesa Juan Luis , Bastos‐González Delfina
Published: May 2012

This work shows that colloidal stability and aggregation kinetics of hydrophobic polystyrene (PS) nanospheres are extremely sensitive to the nature of the salt used to coagulate them. Three PS latices and four aggregating electrolytes, which all share the same cation (Na+) but have various anions located at different positions in the classical Hofmeister series depending on their kosmotropic or chaotropic character, are used. The present study focuses on analyzing different aggregating parameters, such as critical coagulation concentrations (CCC), cluster size distributions (CSD), initial kinetic constants K11, and fractal dimensions of the aggregates df. While aggregation induced by SO42− and Cl− behaved according to the predictions of the classical Derjaguin–Landau–Verwey–Overbeek theory, important discrepancies are found with NO3−, which become dramatic when using SCN−. These discrepancies among the anions were far more significant when they acted as counterions rather than as co‐ions. While SO42− and Cl− trigger fast diffusion‐limited aggregation, SCN− gives rise to a stationary cluster size distribution in a few aggregation times when working with cationic PS particles. Clear differences are found among all analyzed parameters (CCC, CSD, K11, and df), and the experimental findings show that particles aggregate in potential wells whose depth is controlled by the chaotropic character of the anion. This paper presents new experimental evidence that may help to understand the microscopic origin of Hofmeister effects, as the observations are consistent with appealing theoretical models developed in the last few years.
Decision‐making and planning in full recovery of anorexia nervosa
Authors: Lindner Susanne E. , Fichter Manfred M. , Quadflieg Norbert
Published: May 2012

Objective:

Based on findings of persisting neuropsychological impairments in women recovered from anorexia nervosa (rec AN), this study examined decision‐making and planning, for achieving a desired goal, as central executive functions in a large sample of rec AN. The definition of recovery included physiological, behavioral, and psychological variables.

Method:

A total of 100 rec AN women were compared to 100 healthy women, 1:1 matched for age and educational level. Decision‐making was assessed with the Iowa Gambling Task and planning with the Tower of London. Expert interviews and self‐ratings were used for assessing the inclusion/exclusion criteria and control variables.

Results:

Compared to healthy controls, rec AN women were better in decision‐making and worse in planning even after considering control variables.

Discussion:

This study does not support results from other studies showing that rec AN participants perform better in decision‐making. Results from this study show that planning is impaired even after full recovery from AN. © 2012 by Wiley Periodicals, Inc. (Int J Eat Disord 2011;45:866–875)
Copper Complexes of “Superpodal” Amine Ligands and Reactivity Studies towards Dioxygen
Authors: Jozwiuk Anna , Ünal E. Alper , Leopold Stefan , Boyd John P. , Haryono Marco , Kurowski Nadine , Escobar Francisco Velazquez , Hildebrandt Peter , Lach Jochen , Heinemann Frank W. , Wiedemann Dennis , Irran Elisabeth , Grohmann Andreas
Published: May 2012

The results of studies focussed on copper complexes of a variety of ligands with an NN4 donor set are reported. The permethylated tetrapodal ligand 2 forms a complex with copper(I) which, upon reaction with dioxygen at –90 °C, yields a product having a bis(μ‐oxido)dicopper(III) core (“O‐type” product, 10), as inferred from UV/Vis and resonance‐Raman spectroscopic data. The UV/Vis spectrum of 10 has two bands at 300 and 404 nm, with extinction coefficients of 9400 and 10400 L mol–1 cm–1, respectively. Resonance‐Raman spectra display two 16O/18O‐sensitive bands which, based on the isotopic shifts and the absolute frequencies, are attributed to the Cu–O stretching modes of the O‐type product. Complex 10 shows tyrosinase‐like activity, as its reaction with sodium p‐tert‐butylphenolate at –90 °C in THF yields p‐tert‐butylcatechol, in an ortho‐hydroxylation reaction (yield: 30 %). Two new rigid tetrapodal pentadentate ligands (the “superpods” 3 and 4) can be synthesized by condensation of the primary polyamine 1 with paraformaldehyde. Their copper(II) complexes (5 and 6) have been spectroscopically characterized. As ascertained by X‐ray crystallography, 5 has the CuII ion in a tetragonal‐pyramidal environment, with almost uniform Cu–N bond lengths (basal bonds: 2.052 Å and 2.070 Å; apical bond: 2.077 Å). No significant Jahn–Teller distortion is observed here. In 6, the ligand acts as a multinucleating donor, which leads to the formation of a ladder‐like cluster of [Cu(μ3‐OH)] units containing a total of two ligands, six copper(II) ions, four hydroxido ligands and eight trifluoroacetate ions. Two of the trifluoroacetate ions are non‐coordinating. Variable‐temperature magnetic susceptibility data are reported for this hexanuclear copper(II) cluster. Copper(I) complexes of 1 and 3 have been characterized and allowed to react with molecular oxygen, which caused the decomposition of the complexes. The IR spectra of the oxygenation products have bands at 1652 and 1632 cm–1, respectively, which are absent in the spectra of 1 and 3, suggesting that amine functions have been oxidized to imines.
Synthesis, Structure and Property of 5‐Aminotetrazolate Room‐Temperature Ionic Liquids
Authors: Tao Guo‐Hong , Tang Meng , He Ling , Ji Shun‐Ping , Nie Fu‐De , Huang Ming
Published: May 2012

Eight 5‐aminotetrazolate (AT) salts based on the 1,2,3‐trimethylimidazolium (1), 1,3‐dimethylimidazolium (2), 1‐ethyl‐3‐methylimidazolium (3), 1‐butyl‐3‐methylimidazolium (4), 1‐isobutyl‐3‐methylimidazolium (5), 1‐(3′‐methylbutyl)‐3‐methylimidazolium (6), 1‐hexyl‐3‐methylimidazolium (7) and 1‐methyl‐3‐octylimidazolium (8) cations have been synthesized in high yields and fully characterized by IR and NMR spectroscopy and elemental analysis. White plate crystals of 1 were isolated in methanol/diethyl ether and crystallized. Both the AT anion and the 1,2,3‐trimethylimidazolium cation in 1 were delocalized. Differential scanning calorimetry (DSC) combined with thermogravimetric analysis (TGA) tests were used to assess the thermal stabilities of the AT salts. These salts decomposed within the temperature range 230 °C–262 °C. Salts 3–8 are very fluent room‐temperature ionic liquids, whose glass transition temperatures are low. Their viscosities at 30 °C are in the range from 92 cP to 208 cP. A correlation between the viscosity and temperature was found, and the ionic liquids to do not display an Arrhenius temperature behaviour. In addition, the standard enthalpies of formation of salts 1–8 were investigated and analyzed by the theoretical methods. Salt 2 with the 1,3‐dimethylimidazolium cation gave the highest positive enthalpy of formation. For the assessment of the energetic character of the AT salts, impact sensitivities and friction sensitivities were recorded. These AT salts are insensitive to impact (>40 J) and friction (>360 N) confirmed by UN standards. The reactions of these AT salts with 100 % HNO3 were also determined.
Cobalt(II) Complexes Bearing a Bulky N‐Heterocyclic Carbene for Catalysis of Kumada–Tamao–Corriu Cross‐Coupling Reactions of Aryl Halides
Authors: Matsubara Kouki , Sueyasu Tsukasa , Esaki Mariko , Kumamoto Aya , Nagao Shinya , Yamamoto Hitomi , Koga Yuji , Kawata Satoshi , Matsumoto Taisuke
Published: May 2012

Cobalt(II) iodide, bromide, and chloride react with 1 equiv. of IPr [1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene] to form a series of tetrahedral dimeric (30e) complexes of cobalt(II) in good yields. These were transformed into the monomeric forms in the presence of pyridine. These complexes were characterized by SQUID, XPS, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography, and were found to have high catalytic activity for Kumada–Tamao–Corriu cross‐coupling reactions of aryl halides.
Gold(I) Complexes Incorporating Emissive Mercapto‐Pteridine Ligands: Syntheses, X‐ray Structure, Luminescence and Preliminary Cytotoxic Evaluation
Authors: Mullice Lucy A. , Mottram Huw J. , Hallett Andrew J. , Pope Simon J. A.
Published: May 2012

The syntheses of six new mixed P/S‐donor two‐coordinate AuI complexes are described. The complexes incorporate a pteridinyl ligand coordinated through a thiolate donor, and an ancillary tertiary phosphane (PPh3 or PCy3). The mercapto‐pteridine ligands (L1–L3) differ in the nature of the substituents on the pteridine core. An X‐ray crystal structure was obtained for one of the examples, [(L1)Au(PPh3)], revealing weak intermolecular interactions between two molecules of the complex: π–π contacts between aromatic rings appear to support an intermolecular Au–Au contact of approximately 3.05 Å. All of the complexes are luminescent in solution, with emission arising from tuneable ligand‐based excited states, and characterised as a perturbed fluorescence in nature. In this context, complexes of L3 displayed useful visible absorption and emission. Preliminary cytotoxicity assessments were conducted using the MTT assay, and the complexes each displayed impressive anti‐proliferative activities (IC50 < 5 μM) with respect to four different adenocarcinoma cell lines (MCF7, A549, PC3 and LOVO). For a given pteridine moiety, triphenylphosphane appeared to be the co‐ligand of choice for enhancing biological activity.
Zn‐Mediated Synthesis of 3‐Substituted Indoles Using a Three‐Component Reaction Approach
Authors: Anselmo Daniele , Escudero‐Adán Eduardo C. , Martínez Belmonte Marta , Kleij Arjan W.
Published: May 2012

The synthesis of 3‐substituted indoles was investigated through a multicomponent reaction (MCR) approach by using aldehydes, indole and malononitrile as the reagents. The reaction was catalyzed by Lewis acidic Zn(salphen) complexes and their performance was compared with a number of other ZnII structures and M(salphen)s, which showed the Zn(salphen)s to be superior. However, the complex nature of this three‐component reaction (3‐CR) results in substantial byproduct formation that arises from the intermediate benzylidene malononitrile species. The 3‐CR was studied in detail that covered the influence of the base, solvent, reagent stoichiometry and also involved stability studies. The results led to a mechanistic proposal in which the benzylidene malononitrile intermediate plays a central role; it is one of the major species that is formed in most of the catalytic reactions studied. Furthermore, it provided a prelude for the in situ reaction with the malononitrile reagent, which most probably affords a complex mixture of N‐containing heterocycles.
Straightforward Synthesis of Poly(dimethylsiloxane) Phases with Immobilized (1R)‐3‐(Perfluoroalkanoyl)camphorate Metal Complexes and Their Application in Enantioselective Complexation Gas Chromatography
Authors: Spallek Markus J. , Storch Golo , Trapp Oliver
Published: May 2012

A straightforward synthesis of novel chiral polysiloxane‐based metal stationary phases immobilized through a propylenoxy linker (Chirasil‐Metal‐OC3) to the polymeric backbone is presented. Synthesis was accomplished in six steps with high overall yields starting from commercially available, enantiopure (+)‐(1S)‐camphorsulfonic acid. Two different approaches towards Chirasil‐Metal phases featuring either a propylenoxy or propylenthio linker used for immobilization through hydrosilylation are presented. Furthermore, a new protocol for the fluoroacylation, which is one of the key steps in the synthesis of (1R)‐3‐(perfluoroalkanoyl)camphorate metal complexes, was developed to improve the isolation and overall yield. The immobilization of (1R,4S)‐10‐(allyloxy)‐3‐(heptafluorobutanoyl)camphor – 10‐(allyloxy)‐hfbc – onto polysiloxanes as well as the incorporation of nickel(II), oxovanadium(IV), europium(III), and lanthanum(III) was characterized by FT ATR IR and NMR spectroscopy. Overall, seven different Chirasil‐Metal‐OC3polymers with different separation properties were prepared by metal incorporation and variation of the amount of immobilized (1R,4S)‐10‐(allyloxy)‐3‐(heptafluorobutanoyl)camphor (10‐allyloxy‐hfbc: 3.5, 10.2, and 20.0 %). Their performance in enantioselective complexation gas chromatography was systematically studied and excellent enantioselectivity was found for Chirasil‐Nickel‐OC3. Separation of 29 small‐sized compounds, encompassing, among others, epoxides, substituted alkenes and alkynes as well as alcohols and amides, was achieved with high separation factorsα. The synthetic strategy, enantiomer separations and thermal stability (up to 160 °C) demonstrates the versatility of the newly derived Chirasil‐Metal‐OC3phases.
Application of L‐Erythrose‐Derived Nitrones in the Synthesis of Polyhydroxylated Compounds via 3,6‐Dihydro‐2H‐1,2‐oxazine Derivatives
Authors: Jasiński Marcin , Lentz Dieter , Moreno‐Clavijo Elena , Reissig Hans‐Ulrich
Published: May 2012

Enantiopure 3,6‐dihydro‐2H‐1,2‐oxazines were prepared by [3+3] cyclisations starting from lithiated methoxyallene and the L‐erythrose‐derived nitrones 1′ and 3. The role of the side‐chain protective group, which steers the highly selective formation of either anti‐ or syn‐configured products, was demonstrated. A hydroboration/oxidation protocol smoothly converted 1,2‐oxazine derivative syn‐5 into secondary alcohol 6. After deprotection, polyhydroxylated tetrahydro‐2H‐1,2‐oxazine 11, which can be regarded as an azasugar, was isolated. Analogous treatment of 1,2‐oxazine anti‐5 with the borane not only provided the expected secondary alcohol 7, but it also induced reduction of the C=C bond and ring opening. Treatment of syn‐5 and anti‐2 with hydrochloric acid in methanol induced deprotections and cyclisations leading to bicyclic tetrahydro‐2H‐1,2‐oxazine derivatives. The second ring can be either a furan or a pyran ring. In the syn series, furan derivative 12 was formed exclusively, and its hydrogenolysis led to enantiopure aminofuran derivative 14. Acid‐promoted rearrangement of unprotected anti‐2 led to a mixture of bicyclic compounds with furan or pyran rings fused to the 1,2‐oxazine core. However, when TBDPS‐protected compound 20 was used it cleanly led to 1,2‐oxazine 21 with a fused furan ring and then to aminofuran 22. Alternatively, the N–O bond in unprotected anti‐2 was chemoselectively reduced with samarium diiodide, efficiently generating highly functionalized allylic alcohol 23. Acid‐promoted cyclisation and deprotection furnished furan derivative 24. Mechanistic suggestions to explain the different outcomes of the acid‐induced transformations are provided. Overall, it is demonstrated that the stereodivergent addition of lithiated alkoxyallenes to L‐erythrose‐derived nitrones allow flexible access to a series of enantiopure amino polyols, including aminofuran derivatives.
Element profiles in hair and nails of children reflect the uptake from food and the environment
Authors: Oyoo-Okoth Elijah , Admiraal Wim , Osano Odipo , Kraak Michiel H.S.
Published: May 2012

The present study evaluated if the element profiles in hair and nails of children from the Lake Victoria region in Kenya reflect uptake from food and the environment. To this purpose, the element concentrations in hair and nails were related to element concentrations measured in food items, water, and soil. The highest intake of most elements occurred via ingestion of the fish Rastrineobola argentea, which is consumed in higher quantities than other fish and food items. Element concentrations in hair and nails were correlated to food and soil in element-specific patterns. Multivariate analysis combining principal component analysis and multidimensional scaling enabled us to cluster individuals from specific sites and to relate differences between sites to food-consumption patterns and environmental exposures. Site-specific differences in macroelement concentrations among the children were attributed to patterns of food consumption, while those in microelement concentrations reflected differences in geochemical background. It is concluded that the simultaneous analysis of elements in human hair and nails allows separation of populations based on food consumption and geochemical background. Environ. Toxicol. Chem. 2012; 31: 1461–1469. © 2012 SETAC
Effect of light on toxicity of nanosilver to Tetrahymena pyriformis
Authors: Shi Jun-Peng , Ma Chun-Yan , Xu Bin , Zhang Hong-Wu , Yu Chang-Ping
Published: May 2012

More and more silver nanoparticles (AgNPs) have been released into the aquatic environment due to their widespread use, which may result in harmful effects on aquatic organisms. Environmental risk assessments of AgNPs on aquatic organisms in the natural environment (including light, sound, etc.) are indispensable. The aim of the present study was to elucidate the influence of light on the toxicity of AgNPs to Tetrahymena pyriformis. Silver nanoparticles, which were synthesized by reduction of silver nitrate with sodium borohydride, ranged in size from 5 to 20 nm with most particles approximately 10 nm. The authors performed AgNPs toxicity assays under a simulated natural environment with sunlight. The results indicated that the toxicity of AgNPs is higher than silver ion in the environment without light, but under the light condition, the toxicity of AgNPs decreased greatly. After 24 h of incubation with AgNPs, the inhibition ratio was 69.2 ± 7% in the dark and 35.5 ± 2% in the light, and the degree of inhibition was reduced by 33.7%. However, the effect of light on Ag+ could be negligible. Further investigation indicated that the light irradiation could induce the growth of AgNPs and sequentially form bulk agglomeration. This decreased the surface area and the number of bare Ag atoms, resulting in a slower release rate and less Ag+ ions released from AgNPs. At the same time, bulk agglomeration induced the deposition of part of the AgNPs to the aquatic bottom, which decreased the amount of AgNPs existing in water. All these phenomena led to the weakened toxicity of AgNPs in a light irradiation environment. Environ. Toxicol. Chem. 2012; 31: 1630–1638. © 2012 SETAC
Gamma irradiation-induced oxidative stress and developmental impairment in the hermaphroditic fish, Kryptolebias marmoratus embryo
Authors: Rhee Jae-Sung , Kim Bo-Mi , Kang Chang-Mo , Lee Young-Mi , Lee Jae-Seong
Published: May 2012

This study investigated the effects of gamma radiation on the early developmental stages in hermaphroditic fish embryos of Kryptolebias marmoratus. The authors measured reactive oxygen species (ROS) level and antioxidant enzyme activities with the endpoint hatching rate after gamma irradiation of different embryonic stages. Then, the transcriptional changes of antioxidant enzyme-coding genes were evaluated by quantitative real-time reverse transcription polymerase chain reaction in response to gamma radiation on embryonic stages. Gamma radiation inhibited hatching rate and caused developmental impairment in a dose-dependent manner. Embryos showed tolerances in a developmental stage-dependent manner, indicating that early embryonic stages were more sensitive to the negative effects of gamma radiation than were later stages. After 5 Gy rate of radiation, the ROS level increased significantly at embryonic stages 2, 3, and 4 with a significant induction of all antioxidant enzyme activities. The expressions of glutathione S-transferase isoforms, catalase, superoxide dismutase (Mn-SOD, Cu/Zn-SOD), glutathione reductase, and glutathione peroxidase mRNA were upregulated in a dose-and-developmental stage-dependent manner. This finding indicates that gamma radiation can induce oxidative stress and subsequently modulates the expression of antioxidant enzyme-coding genes as one of the defense mechanisms. Interestingly, embryonic stage 1 exposed to gamma radiation showed a decreased expression in most antioxidant enzyme-coding genes, suggesting that this is also related to a lower hatching rate and developmental impairment. The results of this study provide a better understanding of the molecular mode of action of gamma radiation in aquatic organisms. Environ. Toxicol. Chem. 2012; 31: 1745–1753. © 2012 SETAC
Effect of land‐use changes on nonpoint source pollution in the Xizhi River watershed, Guangdong, China
Authors: Xu Kai , Wang Yunpeng , Su Hua , Yang Jingxue , Li Lili , Liu Cang
Published: May 2012

The Annualized Agricultural Non‐point Source (AnnAGNPS) pollution model has been widely used to assess and predict runoff, soil erosion, sediment and nutrient loading with a geographic information system. This article presents a case study of the effect of land‐use changes on nonpoint source (NPS) pollution using the AnnAGNPS model in the Xizhi River watershed, eastern Pearl River Delta of Guangdong province, China. The land‐use changes in the Xizhi River watershed between 1998 and 2003 were examined using the multitemporal remote sensing data. The runoff, soil erosion, sediment transport and nutrient loading 1998 and 2003 were assessed using AnnAGNPS. The effects of land‐use changes on NPS were studied by comparing the simulation results of each year. Our results showed that (i) the NPS loadings increased when forest and grass land converted into paddy, orchard and farmland land, and population size and gross domestic product size as well as the usage amounts of fertilizer and pesticide in the entire watershed were firmly correlated with the NPS loadings; (ii) the land‐use change during fast urbanization in particular when other land types were converted into the development land and buildup land led to increasing of NPS pollution; and (iii) urban land expansion showed more important effects on total organic carbon (TOC) loading compared with nitrogen and phosphorus loadings. Copyright © 2012 John Wiley & Sons, Ltd.
Variation analysis of precipitation during past 286 years in Beijing area, China, using non‐parametric test and wavelet analysis
Authors: Li Miao , Xia Jun , Chen Zhi , Meng Dejuan , Xu Chongyu
Published: May 2012

Non‐parametric methods including Mann–Kendall (M–K) test, continuous wavelet transform (CWT) and discrete wavelet transform analysis are applied in this paper to detect the trend and periodic trait of precipitation data series in Beijing area where the data set spans nearly 300 years from 1724 to 2009. First, the trend of precipitation variables is elaborated by the M–K test (Sequential M–K test). The results show that there is an increasing trend (the value of this trend is 1.98) at the 5%‐significance level and there are not turning points in the whole data series. Then, CWT and wavelet variance are used to check for significant periodic characteristics of data series. In the plots of wavelet transform coefficients and figure of wavelet variance, some periodic events affect the trend of the annual total precipitation series in Beijing area. 85‐year, 35‐year and 21‐year periodic events are found to be the main periodic series of long‐term precipitation data, and they are all statistically significant. Moreover, the results of non‐parametric M–K test are exhibited on seven different combinations of discrete wavelet components. D5 (32‐year periodicity) periodic component is the effective and significant component on data. It is coincident with the result (35‐year periodic event as one part of main periodicity) by using CWT analysis. Moreover, approximation mode shows potential trend of the whole data set because it is the residuals as all periodicities are removed from data series. Thus, the mode A + D5 is responsible for producing a real basic structure of the trend founded on the data. Copyright © 2012 John Wiley & Sons, Ltd.
Landfill disposal of unused medicines reduces surface water releases
Authors: Tischler Lial , Buzby Mary , Finan Douglas S , Cunningham Virginia L
Published: May 2012

The pharmaceutical industry is conducting research to evaluate the pathways and fate of active pharmaceutical ingredients from the consumer to surface waters. One potential pathway identified by the researchers is the disposal of unused pharmaceutical products that are discarded by consumers in household trash and disposed of in municipal solid waste landfills. This study was designed to evaluate relative amounts of surface water exposures through the landfill disposal pathway compared to patient use and flushing of unused medicine pathways. The estimated releases to surface water of 24 example active pharmaceutical ingredients (APIs) in landfill leachate were calculated for 3 assumed disposal scenarios: 5%, 10%, and 15% of the total annual quantity of API sold is discarded and unused. The estimated releases from landfills to surface waters, after treatment of the leachate, were compared to the total amount of each example API that would be released to surface waters from publicly owned treatment works, generated by patient use and excretion. This study indicates that the disposal of unused medications in municipal solid waste landfills effectively eliminates the unused medicine contribution of APIs to surface waters; greater than 99.9% of APIs disposed of in a landfill are permanently retained. Integr Environ Assess Manag 2013; 9: 142–154. © 2012 SETAC
Trends in mortality from leukemia in Europe: An update to 2009 and a projection to 2012
Authors: Bertuccio Paola , Bosetti Cristina , Malvezzi Matteo , Levi Fabio , Chatenoud Liliane , Negri Eva , Vecchia Carlo La
Published: May 2012

We considered trends in mortality from leukemia in Europe over the period 1970–2009 using data from the World Health Organization. We computed age‐standardized (world population) mortality rates, at all ages and in selected age groups, in 11 selected European countries, the European Union (EU) and, for comparative purposes, in the USA and Japan. For the EU, we also provided projections of the mortality to 2012. Over the period considered, mortality from leukemia steadily declined in most European countries in children and young adults, as well as in western and southern Europe at middle‐age (45–69 years); in central/eastern Europe, reductions at ages 45–69 started since the mid‐late 1990s. In the EU, annual percent changes were −3.7% in males and −3.8% in females at age 0–14, −2% in both sexes at age 15–44, and −0.6% in males and −1% in females at middle‐age and overall. No decline was observed at age 70 or more. Between 1997 and 2007, overall EU rates decreased from 5.4 to 4.8/100,000 males and from 3.4 to 2.9/100,000 females. Declines were from 6.2 to 5.5/100,000 males and from 3.7 to 3.2/100,000 females in the USA and from 3.9 to 3.5/100,000 males and from 2.5 to 2.0/100,000 females in Japan. Projected overall rates in the EU at 2012 are 4.3/100,000 males (−11% compared to 2007) and 2.6/100,000 females (−12%).
Getting ready: Results of a randomized trial of a relationship‐focused intervention on the parent–infant relationship in rural early head start
Authors: Knoche Lisa L. , Edwards Carolyn Pope , Sheridan Susan M. , Kupzyk Kevin A. , Marvin Christine A. , Cline Keely D. , Clarke Brandy L.
Published: May 2012

The purpose of this study is to investigate the effects of a relational intervention (the Getting Ready intervention) on parenting behaviors supporting the parent–infant relationship for families enrolled in Early Head Start home‐based programming. Two‐hundred thirty‐four parents and their children participated in the randomized study, with 42% of parents reporting education of less than a high‐school diploma. Brief, semistructured parent–child interaction tasks were videotaped every 4 months over a16‐month intervention period. Observational codes of parent–infant relationship behaviors included quality of three parental behaviors: warmth and sensitivity, support for learning, and encouragement of autonomy; two appropriateness indicators: support for learning and guidance/directives; and one amount indicator: constructive behaviors. Parents who participated in the Getting Ready intervention demonstrated higher quality interactions with their children that included enhanced quality of warmth and sensitivity, and support for their children's autonomy than did parents in the control group. They also were more likely to use appropriate directives with their children and more likely to demonstrate appropriate supports for their young children's learning. Results indicate an added value of the Getting Ready intervention for Early Head Start home‐based programming for families of infants and toddlers.
War trauma lingers on: Associations between maternal posttraumatic stress disorder, parent–child interaction, and child development
Authors: van Ee Elisa , Kleber Rolf J. , Mooren Trudy T.M.
Published: May 2012

Maternal traumatization has been proposed as a risk factor for child development, but the mechanisms involved are poorly understood. This study analyzed the interrelations among maternal posttraumatic stress symptoms, parent–child interaction (emotional availability), and infants' psychosocial functioning and development among 49 asylum‐seeker and refugee mothers and their children (18–42 months). Measures included assessment of mothers' trauma and comorbid symptoms (Harvard Trauma Questionnaire: R.F. Mollica et al., 1992; Hopkins Symptom Checklist: L. Derogatis, R. Lipman, K. Rickels, E. Uhlenhuth, & L. Covi, 1974), emotional availability within parent–child interaction (Emotional Availability Scales: Z. Biringen, 2008), and infants' psychosocial functioning (Child Behavior Checklist: T.M. Achenbach & L.A. Rescorla, 2000) and development (Bayley Scales of Infant Development: B.F. van der Meulen, S.A.J. Ruiter, H.C. Spelberg, & M. Smrkovsky, 2000). The results show that higher levels of maternal posttraumatic stress symptoms are associated with a higher level of psychosocial problems of infants, but not with delays in their mental or psychomotor development. The results also show that higher levels of maternal posttraumatic stress symptoms are associated with higher levels of insensitive, unstructuring, or hostile, but not intrusive, parent–child interactions. Infants show lower levels of responsiveness and involvement to their traumatized mothers. Parent–child interaction did not function as a mediator between maternal trauma symptoms and infants' psychosocial functioning. Results are discussed in relation to the dyad's regulation of emotions. Results implicate a need to reestablish attunement between traumatized mothers and their nontraumatized children.
Mothers' affect dysregulation, depressive symptoms, and emotional availability during mother–infant interaction
Authors: Kim Bo‐Ram , Teti Douglas M. , Cole Pamela M.
Published: May 2012

Maternal affect dysregulation and maternal depressive symptoms were examined as predictors of maternal emotional availability (EA) during mother–infant interaction in a nonclinical sample. In particular, we investigated if affect dysregulation predicts EA and is more important than are depressive symptoms in predicting EA. Questionnaire measures and 30 min of free play were obtained from 46 mothers of 4‐ to 5‐month‐old infants. Mothers' self‐reported affect dysregulation was inversely related to EA, but mothers' depressive symptoms were not related to EA. More specifically, mothers' tendency to use unhealthy externalizing behaviors to reduce tension and distress predicted less EA. These results suggested that even in relatively low‐risk samples, mothers' self‐reported affect dysregulation, particularly the tendency to act out inappropriately in response to tension and distress, may be a more proximal predictor of EA than are depressive symptoms.
Skin innervation at different depths correlates with small fibre function but not with pain in neuropathic pain patients
Authors: Schley M. , Bayram A. , Rukwied R. , Dusch M. , Konrad C. , Benrath J. , Geber C. , Birklein F. , Hägglöf B. , Sjögren N. , Gee L. , Albrecht P.J. , Rice F.L. , Schmelz M.
Published: May 2012

Background

Neuropathy can lead not only to impaired function but also to sensory sensitization. We aimed to link reduced skin nerve fibre density in different levels to layer‐specific functional impairment in neuropathic pain patients and tried to identify pain‐specific functional and structural markers.

Methods

In 12 healthy controls and 36 patients with neuropathic pain, we assessed clinical characteristics, thermal thresholds (quantitative sensory testing) and electrically induced pain and axon reflex erythema. At the most painful sites and at intra‐individual control sites, skin biopsies were taken and innervation densities in the different skin layers were assessed. Moreover, neuronal calcitonin gene‐related peptide staining was quantified.

Results

Perception of warm, cold and heat pain and nerve fibre density were reduced in the painful areas compared with the control sites and with healthy controls. Warm and cold detection thresholds correlated best with epidermal innervation density, whereas heat and cold pain thresholds and axon reflex flare correlated best with dermal innervation density. Clinical pain ratings correlated only with epidermal nerve fibre density (r = 0.38, p < 0.05) and better preserved cold detection thresholds (r = 0.39, p < 0.05), but not with other assessed functional and structural parameters.

Conclusions

Thermal thresholds, axon reflex measurements and assessment of skin innervation density are valuable tools to characterize and quantify peripheral neuropathy and link neuronal function to different layers of the skin. The severity of small fibre neuropathy, however, did not correspond to clinical pain intensity and a specific parameter or pattern that would predict pain intensity in peripheral neuropathy could not be identified.
One‐step radiosynthesis of 4‐[18F]flouro‐3‐nitro‐N‐2‐propyn‐1‐yl‐benzamide ([18F]FNPB): a new stable aromatic porosthetic group for efficient labeling of peptides with fluorine‐18
Authors: Li Yesen , Liu Yaqin , Zhang Lan , Xu Yuhong
Published: May 2012

4‐[18F]flouro‐3‐nitro‐N‐2‐propyn‐1‐yl‐benzamide ([18F]FNPB) was developed as a new stable aromatic prosthetic group for more efficient click labeling of peptides. A new aromatic precursor 3,4‐dinitro‐N‐2‐propyn‐1‐yl‐benzamide was radiofluorinated using [18F]KF/K2.2.2 followed by HPLC purification to obtain the desired product [18F]FNPB. [18F]FNPB was synthesized with a 58% radiochemical yield, a specific activity > 350 GBq/µmol, and radiochemical purity was exceeded 98% in 40 min. The in vitro stability studies showed no detectable radiodefluorination over 2 h in mouse plasma. The click labeling yield of three different peptides with [18F]FNPB were all above 87%. The in vitro study suggests that [18F]FNPB may be stable in vivo and could have general application in labeling peptides with high radiochemical yield for positron emission tomography applications. Copyright © 2012 John Wiley & Sons, Ltd.
Nitrogen fluxes during the initial stage of willows and poplars in short‐rotation coppices
Authors: Balasus Antje , Bischoff Wolf‐Anno , Schwarz Andreas , Scholz Volkhard , Kern Jürgen
Published: May 2012

Among energy crops, short‐rotation coppices (SRC) are recommended to provide renewable energy. Compared to annual crops, willows and poplars are regarded as plants with low requirements for nutrients, herbicides, pesticides, and soil maintenance. However, only little is known about N‐fertilizer effects on SRC and the few studies are even inconsistent. Therefore, we studied the effects of N on yields of willows and poplars in a field experiment. The effects of N fertilization on nitrate leaching and nitrous oxide emissions from the loamy‐sand soil were also measured. Cuttings of willows (Salix viminalis clone Inger) and poplars (Populus maximovizcii × P. nigra clone max 4) were planted on farmland in 2008. The experiment was arranged in a random block design with three levels of N fertilizer (0, 50, and 75 kg N ha–1 y–1). After 2 y, the trees were harvested for the first time. Fertilization did not affect the yields of willows or poplars. However, the application of 75 kg N ha–1 y–1 caused an average increase of N leaching in the willow and poplar plots of 25 kg N ha–1 y–1 and 40 kg N ha–1 y–1, respectively. Emissions of N2O were increased by a maximum of only 0.2 kg N ha–1 y–1. Further, the N fertilizer stimulated the growth of the weed biomass in case of the willow plots by 46% and of the weed N content by 52% (r = 0.53). In conclusion, in the first 2 y, SRC could be produced in a more effective and environmentally friendly manner without mineral fertilizer.
Analysis of soil fertility and its anomalies using an objective model
Authors: Moral Francisco J. , Rebollo Francisco J. , Terrón José M.
Published: May 2012

In this work, the use of an objective method, the formulation of the Rasch measurement model, which synthesizes data with different units into a uniform analytical framework, is considered to get representative measures of soil fertility potential in an experimental field. Thus, two types of information about the soil were obtained from soil samples taken at 70 locations: first, the textural components were determined, and, secondly, deep (ECa‐90) and shallow (ECa‐30) soil apparent electrical conductivity, approximately 0–90 and 0–30 cm depths, respectively, were measured. A latent variable, denominated soil fertility potential, was defined. It is supposed, and later it is verified, that all soil properties previously indicated have a marked influence on the latent variable. The adequate assignment of categorical values across properties measures and the good fit of the data are checked as a previous phase to properly compute the Rasch measures. After applying the Rasch methodology, it was obtained that both electrical conductivities are the most influential properties on soil fertility potential, getting moreover a ranking of all soil samples according to their fertility potential and the unexpected behaviors, called misfits, of some soil samples, which constitute a very useful information to better match soil and crop requirements as they vary in the field, being a rational basis for a site‐specific crop management.
Dye attached poly(hydroxyethyl methacrylate) cryogel for albumin depletion from human serum
Authors: Andac Muge , Galaev Igor , Denizli Adil
Published: May 2012

Cibacron Blue F3GA was immobilized on poly(hydroxyethyl methacrylate) cryogel and it was used for selective and efficient depletion of albumin from human serum. The poly(hydroxyethyl methacrylate) was selected as the basic component because of its inertness, mechanical strength, chemical and biological stability, and biocompatibility. Cibacron Blue F3GA was covalently attached to the poly(hydroxyethyl methacrylate) cryogel to produce poly(hydroxyethyl methacrylate)‐Cibacron Blue F3GA cryogel affinity column. The poly(hydroxyethyl methacrylate)‐Cibacron Blue F3GA cryogel was characterized with respect to gelation yield, swelling degree, total volume of macropores, Fourier Transform Infrared spectroscopy, and scanning electron microscopy. It was found that the maximum amount of adsorption (343 mg/g of dry cryogel) obtained from experimental results is very close to the calculated Langmuir adsorption capacity (345 mg/g of dry cryogel). The maximum adsorption capacity for poly(hydroxyethyl methacrylate)‐Cibacron Blue F3GA cryogel column was obtained as 950 mg/g of dry cryogel for nondiluted serum. The adsorption capacity decreased with increasing dilution ratios while the depletion ratio of albumin remained as 77% in serum sample. Finally, the poly(hydroxyethyl methacrylate)‐Cibacron Blue F3GA cryogel was optimized for using in the fast protein liquid chromatography system for rapid removal of the high abundant proteins from the human serum.
Tracking antiangiogenic components fromGlycyrrhiza uralensisFisch. based on zebrafish assays using high‐speed countercurrent chromatography
Authors: Han Liwen , Yuan Yanqiang , Zhao Liang , He Qiuxia , Li Yubo , Chen Xiqiang , Liu Xiuhe , Liu Kechun
Published: May 2012

Natural products are some of the most important sources of lead compounds for drug discovery. The advanced isolation technique of lead compounds of natural origin using therapeutically relevant bioassays is capable of enhancing work efficiency from complex multiconstituent extracts. In the present study, a bioassay‐guided isolation strategy combined with bioactivity screening was used to identify novel angiogenesis inhibitors from licorice (Glycyrrhiza uralensisFisch.) based on the zebrafish model and rapid preparative separation by high‐speed countercurrent chromatography. Zebrafish embryos at 24 h postfertilization were chosen as the angiogenesis inhibition model for bioactivity screening. A solvent system (n‐hexane–ethyl acetate–methanol–water) with different ratios was optimized and applied in the high‐speed countercurrent chromatography separation of two fractions,Fr5 andFr6, from the ethyl acetate extract of licorice. Blood circulation and vascular outgrowth in intersegmental vessels were found to be simultaneously inhibited by isoliquiritigenin and isolicoflavonol in a dose‐dependent manner. Thus, these two compounds were identified and considered as active inhibitors against angiogenesis. These experimental results indicate that zebrafish bioassays combined with high‐speed countercurrent chromatography may provide an alternative pathway for the rapid isolation of bioactive natural products.
Adsorbents and columns in analytical high‐performance liquid chromatography: A perspective with regard to development and understanding
Authors: Unger Klaus K. , Liapis Athanasios I.
Published: May 2012

A brief historical survey is presented on the evaluation of silica adsorbents in analytical HPLC. The theory of analytical HPLC is mostly still being based on the height equivalent to a theoretical plate concept and the van Deemter equation that was derived from gas phase adsorption involving a linear adsorption isotherm and fast mass transfer kinetics. One can obviously wonder whether the use of the van Deemter equation is relevant and valid for the evaluation of the performance of HPLC systems, where most often the liquid solutes involve charged molecules in electrolytes and in very many cases the adsorbates are macromolecules having diffusion coefficients of small magnitude. Instead of the van Deemter equation, a multi‐scale modelling approach that involves microscopic and macroscopic dynamic non‐linear mass‐transfer‐rate models should be employed. Furthermore, advanced experimental methods for the characterisation of porous media and the distribution of the density of immobilised active sites (e.g., ligands) on surfaces as well as microscopic pore–network modelling and molecular dynamics modelling and simulation methods could be used for the design of novel adsorbents whose porous structures and immobilised active sites would provide effective mass transport and adsorption rates for realising efficient separations as well as high dynamic capacities when larger throughputs are required.
Remarkable Groups of Graphs with Edge Colourings
Authors: Baumann Ulrike , Lesch Manfred , Schmeichel Irmgard
Published: May 2012

Every edge colouring of a graph G determines permutation groups on the vertex set of G. Groups of colour preserving automorphisms and groups of partition preserving automorphlums are especially interesting. The paper deals with relations between these groups and a permutation group investigated by N. L. Biggs.
An Iteration Method for Bifurcation Problem Involving Fredholm Mappings
Authors: Tan Nguyen Xuan
Published: May 2012

Using the idea of the Liapunov‐Schmidt procedure and the modification of the Seidel‐Newton methods we show the existence of bifurcation solutions of equations of the form

Let λ be a characteristic value of the pair (T, L) (i.g. T(u) = L(λ, u.) for some u ± 0). Under sufficient conditions on T, L, H we prove by a constructive method that (λ, 0) is a bifurcation solution of the above equations. Furthermore, we obtain an analytical form of a parametric family of nontrivial solutions in a neighborhood of (λ, 0).
Fundamental Theorems of Calculus for Packing Measures on the Real Line
Authors: Haase H.
Published: May 2012

The fundamental Theorems of Calculus are extended to the treatment of packing measures on the real line. These are related to the corresponding result for Hausdorff measures. We prove that the centered inner‐envelope derivative and the outer‐envelope derivative of a continuous increasing function on an interval differ, but in a certain sense they are almost everywhere linear and the theorems are true for h‐continuous almost h‐singular functions of bounded variation.
The Structure of the Spectrum of Fourth‐Order Differential Operators with Random Coefficients
Authors: Teichert H.
Published: May 2012

In this paper it is proved that under certain conditions on the coefficients the random operator H = \documentclass{article}\pagestyle{empty}\begin{document}$H = \frac{1}{{r\left( {x_t } \right)}}\left[ {\frac{{d^2 }}{{dt^2 }}\left( {\frac{1}{{p\left( {x_t } \right)}}\frac{{d^2 }}{{dt^2 }}} \right) + q\left( {x_t } \right)} \right], \in R^1$\end{document} being a stationary, ergodic Markov process with compact State space K, has almost surely pure point spectrum and exponentially decreasing eigenfunctions. The method used here can be extended to operators corresponding to certain matrix Sturm‐Liouville problems.