Characterization and properties of metallic iron nanoparticles: spectroscopy, electrochemistry, and kinetics

There are reports that nano-sized zero-valent iron (Fe0) exhibits greater reactivity than micro-sized particles of Fe0, and it has been suggested that the higher reactivity of nano-Fe0 may impart advantages for groundwater remediation or other environmental applications. However, most of these reports are preliminary in that they leave a hostof potentiallysignificant(and often challenging) material or process variables either uncontrolled or unresolved. In an effort to better understand the reactivity of nano-Fe0, we have used a variety of complementary techniques to characterize two widely studied nano-Fe0 preparations: one synthesized by reduction of goethite with heat and H2 (Fe(H2)) and the other by reductive precipitation with borohydride (Fe(BH)). Fe(H2) is a two-phase material consisting of 40 nm alpha-Fe0 (made up of crystals approximately the size of the particles) and Fe3O4 particles of similar size or larger containing reduced sulfur; whereas Fe(BH) is mostly 20-80 nm metallic Fe particles (aggregates of <1.5 nm grains) with an oxide shell/coating that is high in oxidized boron. The FeBH particles further aggregate into chains. Both materials exhibit corrosion potentials that are more negative than nano-sized Fe2O3, Fe3O4, micro-sized Fe0, or a solid Fe0 disk, which is consistent with their rapid reduction of oxygen, benzoquinone, and carbon tetrachloride. Benzoquinone-which presumably probes inner-sphere surface reactions-reacts more rapidly with FeBH than Fe(H2), whereas carbon tetrachloride reacts at similar rates with FeBH and Fe(H2), presumably by outer-sphere electron transfer. Both types of nano-Fe0 react more rapidlythan micro-sized Fe0 based on mass-normalized rate constants, but surface area-normalized rate constants do not show a significant nano-size effect. The distribution of products from reduction of carbon tetrachloride is more favorable with Fe(H2), which produces less chloroform than reaction with Fe(BH).     

A prospective study on the behavior of pediatric intensive care unit nurses, concerning the care given to suicidal children

Pediatric intensive care units use sophisticated medical technology and are staffed by deeply committed nurses who are subjected to significant psychological stress. This stress varies with the type of patient and influences the style and quality of care. With this respect, children and adolescents admitted after a suicidal attempt are considered catalysts. However, there have been no systematic studies of how pediatric intensive care nurses respond emotionally to their interactions with these patients. This epidemiological study conducted in five Parisian Teaching Hospital pediatric intensive care units used a specially designed questionnaire to evaluate nurses' responses on the basis of style of care. Children under 16 years of age admitted after attempted suicide were studied comparatively with same age children admitted for status asthmaticus or encephalopathy with seizures. Results highlighted the differences in nurses' psychological responses to these situations and their difficulties in interacting with patients. This study provides strict methodological guidelines for investigating an issue often discussed emotionally or on the basis of anecdotal data.     

Engineered Bacterial Flavin-Dependent Monooxygenases for the Regiospecific Hydroxylation of Polycyclic Phenols

4-Hydroxyphenylacetate 3-hydroxylase (4HPA3H), a flavin-dependent monooxygenase from E. coli that catalyzes the hydroxylation of monophenols to catechols, was modified by rational redesign to convert also more bulky substrates, especially phenolic natural products like phenylpropanoids, flavones or coumarins. Selected amino acid positions in the binding pocket of 4HPA3H were exchanged with residues from the homologous protein from Pseudomonas aeruginosa, yielding variants with improved conversion of spacious substrates such as the flavonoid naringenin or the alkaloid mimetic 2-hydroxycarbazole. Reactions were followed by an adapted Fe(III)-catechol chromogenic assay selective for the products. Especially substitution of the residue Y301 facilitated modulation of substrate specificity: introduction of nonaromatic but hydrophobic (iso)leucine resulted in the preference of the substrate ferulic acid (having a guaiacyl (guajacyl) moiety, part of the vanilloid motif) over unsubstituted monophenols. The in vivo (whole-cell biocatalysts) and in vitro (three-enzyme cascade) transformations of substrates by 4HPA3H and its optimized variants was strictly regiospecific and proceeded without generation of byproducts.     

Reduction of polyhalogenated methanes by surface-bound Fe(II) in aqueous suspensions of iron oxides

Uptake of ferrous iron from aqueous solution by iron oxides results in the formation of a variety of reactive surface species capable of reducing polyhalogenated methanes (PHMs). Pseudo-first-order reaction rate constants, k(obs), of PHMs increased in the order CHBrCl2 < CHBr2Cl < CHBr3 < CCl4 < CFBr3 < CBrCl3 < CBr2Cl2. The k(obs) values increased with the exposure time, teq, of Fe(II) to suspended iron oxides which was attributed to the rearrangement of initially sorbed Fe(II) species to more reactive surface species with time. At pH 7.2, the k(obs) values of PHMs also increased with the concentration of surface-bound ferrous iron, Fe(II)sorb, particularly when Fe(II)tot was increased to concentrations where surface precipitation becomes likely. At fixed total Fe(II) concentrations, k(obs) values increased exponentially with pH. The highest reactivities were associated with pH conditions where surface precipitation of Fe(II) is expected. Fe(II)sorb and pH, however, had opposite effects on the product formation of PHMs. At pH 7.2, the formation of formate from CX4 (X = CI, Br) increased with Fe(II)sorb, whereas increasing pH favored the formation of CHX3. The ratio of halogenated products and formate formed is indicative of the relative importance of initial one- or two-electron-transfer processes, respectively, and was found to depend on the type of iron oxide mineral also. Our data form a basis to assess the importance of chemical reactions in natural attenuation processes of PHMs in environmental systems under iron-reducing conditions.     

Enemies and Friends in the Neighborhood: Orthographic Similarity Effects in Semantic Categorization.

Studies investigating orthographic similarity effects in semantic tasks have produced inconsistent results. The authors investigated orthographic similarity effects in animacy decision and in contrast with previous studies, they took semantic congruency into account. In Experiments 1 and 2, performance to a target (cat) was better if a previously studied neighbor (rat) was congruent (i.e., belonged to the same animate-inanimate category) than it was if it was incongruent (e.g., mat). In Experiments 3 and 4, performance was better for targets with more preexisting congruent neighbors than for targets with more preexisting incongruent neighbors. These results demonstrate that orthographic similarity effects in semantic categorization are conditional on semantic congruency. This strongly suggests that semantic information becomes available before orthographic processing has been completed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Inhibition from nonword primes in lexical decision reexamined: The critical influence of instructions.

Compound-cue theory predicts that lexical decisions are slower to word targets preceded by a nonword than to word targets preceded by an unrelated word. This nonword-prime inhibition effect is not predicted by spreading-activation theories. R. Ratcliff and G. McKoon (1995) obtained nonword-prime inhibition, whereas T. R McNamara (1994b) failed to obtain it. In the present study, for both a 200-ms and 350-ms prime-target stimulus onset asynchrony, nonword-prime inhibition was obtained for participants who, as in Ratcliff and McKoon's research, received instructions that mentioned that prime and target could be related. No nonword-prime inhibition was found for participants who, as in McNamara's research, received instructions that did not mention the possibility of a prime-target relation. Neither compound cue nor spreading activation can explain this pattern. The possibility that nonword-prime inhibition results from response competition is discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Synthesis and Inhibition Activity Study of Triazinyl-Substituted Amino(alkyl)-benzenesulfonamide Conjugates with Polar and Hydrophobic Amino Acids as Inhibitors of Human Carbonic Anhydrases I,II, IV,IX, and XII

Primary sulfonamide derivatives with various heterocycles represent the most widespread group of potential human carbonic anhydrase (hCA) inhibitors with high affinity and selectivity towards specific isozymes from the hCA family. In this work, new 4-aminomethyl- and aminoethyl-benzenesulfonamide derivatives with 1,3,5-triazine disubstituted with a pair of identical amino acids, possessing a polar (Ser, Thr, Asn, Gln) and non-polar (Ala, Tyr, Trp) side chain, have been synthesized. The optimized synthetic, purification, and isolation procedures provided several pronounced benefits such as a short reaction time (in sodium bicarbonate aqueous medium), satisfactory yields for the majority of new products (20.6–91.8%, average 60.4%), an effective, well defined semi-preparative RP-C18 liquid chromatography (LC) isolation of desired products with a high purity (>97%), as well as preservation of green chemistry principles. These newly synthesized conjugates, plus their 4-aminobenzenesulfonamide analogues prepared previously, have been investigated in in vitro inhibition studies towards hCA I, II, IV and tumor-associated isozymes IX and XII. The experimental results revealed the strongest inhibition of hCA XII with low nanomolar inhibitory constants (K_is) for the derivatives with amino acids possessing non-polar side chains (7.5–9.6 nM). Various derivatives were also promising for some other isozymes.     

Metal-based nanoparticle synthesis from the rapid expansion of carbon dioxide solutions

Synthesis of 10 to 500 nm diameter Fe-based nanoparticles is described. Nanometer-sized droplets of iron carbonyl are generated by the rapid expansion of CO2-based supercritical fluid solutions and are photolyzed in-flight using a UV lamp to remove the carbonyl groups. Solid metal particles are collected electrostatically as coatings or loose particle aggregates on solid surfaces. Upon air oxidation, the iron particles react rapidly to produce an iron oxide phase. Mo-based nanoparticles were similarly produced using a Mo(Co)6 precursor. FTIR analysis of collected nanoparticles suggests that carbonyl groups are more readily photolyzed from the Fe precursor than from the Mo analog.     

No retrieval-induced forgetting using item-specific independent cues: Evidence against a general inhibitory account.

Retrieval practice with particular items from memory can impair the recall of related items on a later memory test. This retrieval-induced forgetting effect has been ascribed to inhibitory processes (M. C. Anderson & B. A. Spellman, 1995). A critical finding that distinguishes inhibitory from interference explanations is that forgetting is found with independent (or extralist) cues. In 4 experiments, the authors tested whether the forgetting effect is cue-independent. Forgetting was investigated for both studied and unstudied semantically related items. Retrieval-induced forgetting was not found using item-specific independent cues for either studied or unstudied items. However, forgetting was found for both item types when studied categories were used as cues. These results are not in line with a general inhibitory account, because this account predicts retrieval-induced forgetting with independent cues. Interference and context-specific inhibition are discussed as possible explanations for the data. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Phase estimation of visual evoked responses

The phase of visual evoked responses (VERs) is one of the basic parameters in functional diagnostics of the visual system. A new method for phase estimation of VERs based on the observer model in system identification is introduced. Simulated data show significantly less variance of estimation than actual estimators do. By means of the new estimator, the dynamics of the visual system according to selected optical stimuli has been analyzed.