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Accumulation of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) in indigenous and agricultural plants grown in HMX-contaminated anti-tank firing-range soil.

To investigate their potential for phytoremediation, selected agricultural and indigenous terrestrial plants were examined fortheir capacity to accumulate and degrade the explosive octahydro-1 ,3,5,7-tetra nitro-1,3,5,7-tetrazocine (HMX). Plant tissue and soil extracts were analyzed for the presence of HMX and possible degradative metabolites using high-performance liquid chromatography with diode-array UV detection (HPLC-UV), micellar electrokinetic chromatography with diode-array UV detection (MEKC-UV), and HPLC with electrospray ionization mass spectrometry (LC-MS). The pattern of HMX accumulation for alfalfa (Medicago sativa), bush bean (Phaseolus vulgaris), canola (Brassica rapa), wheat (Triticum aestivum), and perennial ryegrass (Loliumperenne) grown in a controlled environment on contaminated soil from an anti-tank firing range was similar to that observed for plants (wild bergamot (Monarda fistulosa), western wheat grass (Agropyron smithii), brome grass (Bromus sitchensis), koeleria (Koeleria gracilis), goldenrod (Solidago sp.), blueberry (Vaccinium sp.), anemone (Anemone sp.), common thistle (Circium vulgare), wax-berry (Symphoricarpos albus), western sage (Artemisia gnaphalodes), and Drummond's milk vetch (Astragalus drummondii)) collected from the range. No direct evidence of plant-mediated HMX (bio)chemical transformation was provided by the available analytical methods. Traces of mononitroso-HMX were found in contaminated soil extracts and were also observed in leaf extracts. The dominant mechanism for HMX translocation and accumulation in foliar tissue was concluded to be aqueous transpirational flux and evaporation. The accumulation of HMX in the leaves of most of the selected species to levels significantly above soil concentration is relevant to the assessment of both phytoremediation potential and environmental risks.

Azocines↗

A New Binucleating Ligand Based on Anthracene and Its Cofacial Dirhodium(I) and Diiridium(I) Complexes.

A new bis(beta-keto enamine) ligand (2a, ABIH(2)) containing a 1,8-anthracenediyl bridging group has been synthesized by a four-step procedure that relies on the Pd-catalyzed cross-coupling between (3,5-dimethylisoxazol-4-yl)trialkyltin and 1,8-dibromoanthraquinone or -anthracene. The molecular structures of the 1,8-bis(3,5-dimethylisoxazol-4-yl)anthraquinone (8) and -anthracene (10) intermediates were determined by X-ray analysis. Crystal data for 8: orthorhombic, space group Pbca; a = 14.351 (2), b = 11.932 (1), c = 23.278 (2) Å; V = 3986 (1) Å(3); Z = 8; R = 0.057 for 2615 reflections. Crystal data for 10: orthorhombic, space group P2(1)2(1)2(1); a = 7.104 (1), b = 12.805 (1), c = 22.280 (2) Å; V = 2026.7 (6) Å(3); Z = 4; R = 0.066 for 3423 reflections. The rigid ABIH(2) ligand, whose chelating moieties are constrained to be cofacial, allows the preparation of a new family of cofacial bimetallic complexes (ABI)[ML(2)](2) with controllable environments around the metal centers. Two novel cofacial binuclear complexes 4 and 5, with ML(2) = dicarbonylrhodium(I) and (eta(4)-1,5-cyclooctadiene)iridium(I), have been synthesized by reaction of ABIH(2) with [(&mgr;-Cl)Rh(CO)(2)](2) and [(&mgr;-Cl)Ir(COD)](2), respectively. NMR data indicate the formation of meso and racemic atropisomers for 2a, 4, and 5.

Journal Article↗

Degradation of sulfosulfuron, a sulfonylurea herbicide, as influenced by abiotic factors.

A laboratory experiment was conducted to study the stability of sulfosulfuron [1-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2yl) urea] in a controlled environment of pH, temperature, solvent, and surface. In another experiment the photostability of sulfosulfuron was studied after irradiation under sunlight. Under alkaline condition, it yielded 1-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-yl-3-(4,6-dimethoxypyrimidin-2-yl) amine, and under acidic condition it degraded to 1-(2-ethylsulfonylimidazo[1,2-a] pyridin)-3-sulfonamide and 4,6-dimethoxy-2-aminopyrimidine. Photodegradation included breaking of a sulfonylurea bridge, as in the case of acidic hydrolysis and contraction of the sulfonylurea bridge was the major pathway of alkaline hydrolysis.

Drug Stability↗

Application of high-Cu compost to dill and peppermint.

A controlled environment experiment was conducted to determine the effect of amending soil with various rates of high-Cu compost (0, 20, 40, and 60% compost/soil by volume) on dill (Anethum graveolens L.) and peppermint (Mentha X piperita L.) yields, on fractionation of Cu and Zn in soils, on elemental composition of soil and tissue, and on the essential oils. The compost contained about 2000 mg kg(-)(1) of Cu. Dill yields were greatest in the 20 or 40% treatments, but peppermint yields were greatest in the 20% treatment. Compost additions increased soil pH and electrical conductivity (EC), HNO(3) extractable soil B, Ca, K, Mg, Mn, P, S, Na, and Pb. Additions of high-Cu compost to soil increased tissue P, S, and Na in both crops and Mn, Mo, and Zn in dill but decreased tissue Ca, Cd, and Fe in both crops and Mn, Mo, and Zn in peppermint, increased Cu in all soil fractions including exchangeable, and increased tissue Cu of dill and peppermint as compared to unamended soil. Addition of 60% of high-Cu compost to soil resulted in 760-780 mg kg(-)(1) Cu in the growth medium. Nevertheless, Cu content in both crops reached only 12 mg kg(-)(1) DW in the 60% compost treatment, which is below the toxicity levels for plants and below the upper chronic dietary exposure for animals. The application of high-Cu compost altered chemical composition of dill and peppermint essential oils, but oils were free of Cu, Zn, Cd, Ni, Cr, and Pb. Results from this study suggest that mature composts with concentrations of Cu and Zn of 2008 and 321 mg/kg, respectively, can be used as a soil conditioner without risk for phytotoxicity or risk of increasing the normal range of Cu and Zn in crop tissue. However, the long-term effect of the accumulation of heavy metals in soils following repeated compost applications needs to be carefully considered.

Anethum graveolens↗

Analysis of gamma-irradiated melon, pumpkin, and sunflower seeds by electron paramagnetic resonance spectroscopy and gas chromatography-mass spectrometry.

Seeds of melon (Citrullus lanatus var. sp.), pumpkin (Cucurbita moschata), and sunflower (Heliantus annus) were gamma-irradiated at 1, 3, 5, and 10 kGy and analyzed by electron paramagnetic resonance (EPR) and gas chromatography-mass spectrometry (GC-MS) according to EN1787:2000 and EN1785:2003, respectively. Distinguishable triplet signals due to the presence of induced cellulose radicals were found at 2.0010-2.0047 g in the EPR spectra. The gamma-irradiated radiolytic markers of 2-dodecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) were identified in all irradiated seed samples. Both the free radicals and the alkylcyclobutanones were found to increase with irradiation dose. In general, linear relationships between the amount of radicals and irradiation dosage could be established. Studies at an ambient temperature (20-25 degrees C) in a humidity-controlled environment showed a complete disappearance of the cellulosic peaks for irradiated samples upon 60 days of storage. Such instability behavior was considered to render the usefulness of using EPR alone in the determination of irradiated seed samples. On the other hand, 2-DCB and 2-TCB were also found to decompose rapidly (>85% loss after 120 days of storage), but the radiolytic markers remained quantifiable after 120 days of postirradiation storage. These results suggest that GC-MS is a versatile and complimentary technique for the confirmation of irradiation treatment to seeds.

Cucurbita↗

Metabolism-based resistance of a wild mustard (Sinapis arvensis L.) biotype to ethametsulfuron-methyl.

Under controlled-environment conditions, ethametsulfuron-methyl doses that inhibited growth by 50% (ED(50)) were >100 and <1 g of active ingredient (ai) ha(-)(1) for ethametsulfuron-methyl-resistant (R) and -susceptible (S) wild mustard, respectively. There were no differences between the two biotypes with regard to absorption and translocation of the herbicide. Three days after treatment, approximately 90, 5, and 2% of the applied [(14)C]ethametsulfuron-methyl was found in the treated leaf, foliage, and roots of each biotype, respectively. Acetolactate synthase extracted from the two biotypes was equally sensitive to both ethametsulfuron-methyl and chlorsulfuron. These results indicate that resistance was not due to differences in the target site, absorption, or translocation. However, ethametsulfuron-methyl was metabolized more rapidly in the R than the S biotype. Approximately 82, 73, 42, 30, and 17% of the recovered radioactivity remained as ethametsulfuron-methyl in R wild mustard 3, 6, 18, 48, and 72 h after treatment, respectively. Conversely, 84, 79, 85, and 73% of the (14)C was ethametsulfuron-methyl in the S biotype 12, 24, 48, and 72 h after treatment, respectively. On the basis of these results, it is proposed that resistance is due to enhanced metabolism of ethametsulfuron-methyl in the R biotype.

Absorption↗

Isolation of halogenated monoterpenes from bioreactor-cultured microplantlets of the macrophytic red algae Ochtodes secundiramea and Portieria hornemannii.

Field collections of the red macroalgae Ochtodes secundiramea and Portieria hornemannii exhibit site-to-site variations in halogenated monoterpene (HMT) content. In contrast, microplantlets of O. secundiramea and P. hornemannii established through cell and tissue culture techniques had remarkably similar HMT profiles when cultivated in a photobioreactor under identical, controlled conditions. Both algae shared Apakaochtodene B (6) as the only cyclic HMT, 10E-bromomyrcene (3) and 10E-bromo-3-chloro-alpha-myrcene (4) as the dominant acyclic HMTs, and myrcene (1) as their common precursor. Furthermore, HMT yields were comparable between organisms (0.9-1.3 micromol/g dry mass of 6; 3.4-4.4 micromol/g of 3). P. hornemannii microplantlets also contained 7-chloromyrcene (9) as the dominant compound (37-73 micromol/g), suggesting additional chlorination capacity. Proposed pathways for HMT biosynthesis shared by P. hornemannii and O. secundiramea microplantlets possessed two common manifolds: (a) bromonium ion (Br(+))-catalyzed cyclization of 1, followed by chlorination to yield 6; (b) Markovnikov addition of Br(+) at Delta(6,10) of 1 to yield 3 with a marked selectivity (>50:1) for the E isomer, followed by chlorination of 3 to 4. This study demonstrated that bioreactor tissue culture is a new venue for bioprospecting and production of natural compounds from marine macroalgae under a controlled environment.

Catalysis↗

Proteome analysis of isolated perfused organ effluent as a novel model for protein biomarker discovery.

The discovery of novel serological biomarkers is critical for improving disease diagnosis and monitoring treatment response. Proteomic analysis of model systems, such as isolated cells in culture and patient plasma and serum, represents the current state-of-the-art. Here, we coupled proteomics with isolated organ perfusion, which allows a disease state to be studied in a physiologic, yet controlled, environment. Potential markers specific to the disease or to changes in the surrounding tissue may be discovered. The effectiveness of this model was evaluated using proteomic analysis of effluent fractions collected from isolated beating rat hearts during reperfusion after brief episodes of ischemia. The detection of clinical markers for myocardial ischemia in this effluent was robust and analytically straightforward, validating the potential of isolated organ perfusion in diagnostic protein discovery.

Animals↗

Physiological levels of C-reactive protein in normal canine sera.

This study was undertaken to investigate whether the level of C-reactive protein (CRP) in the serum of dogs undergoes physiological variation, using 10 normal Beagle dogs (5 males and 5 females), 1-2 years old, maintained in a healthy condition in a controlled environment. The CRP concentration in the sera collected seven times each day at intervals of approximately 3 h ranged from 0.8 to 16.4 micrograms/ml (mean 5.06 +/- 3.60) in one experiment and from 0.8 to 14.0 micrograms/ml (mean 4.50 +/- 2.80) in a second experiment. On examining the 24-h variations in the concentration of CRP in serum, neither consistent changes nor a definite pattern of circadian rhythm was detected. During 28 days observation, only very slight changes, which seemed attributable to analytical errors, were seen in any of the dogs, except one. The concentration of CRP in the serum during the 28 days ranged from 0.8 to 22.6 micrograms/ml (mean 3.65 +/- 1.40). The concentrations underwent no significant variations in individual dogs, but significant differences were found between the dogs (p < 0.01).

Animals↗

Voice loops as coordination aids in space shuttle mission control.

Voice loops, an auditory groupware technology, are essential coordination support tools for experienced practitioners in domains such as air traffic management, aircraft carrier operations and space shuttle mission control. They support synchronous communication on multiple channels among groups of people who are spatially distributed. In this paper, we suggest reasons for why the voice loop system is a successful medium for supporting coordination in space shuttle mission control based on over 130 hours of direct observation. Voice loops allow practitioners to listen in on relevant communications without disrupting their own activities or the activities of others. In addition, the voice loop system is structured around the mission control organization, and therefore directly supports the demands of the domain. By understanding how voice loops meet the particular demands of the mission control environment, insight can be gained for the design of groupware tools to support cooperative activity in other event-driven domains.

Communication↗

Analysis methods of polysorbate 20: A new method to assess the stability of polysorbate 20 and established methods that may overlook degraded polysorbate 20.

PURPOSE: Polysorbate 20 is a commonly used excipient in biopharmaceutical formulations, some of which may have an enzymatic activity. The action(s) of polysorbate 20 in biopharmaceutical formulations as a stabilizer require this surfactant to maintain its intact structure. This manuscript evaluates a new analytic method for the analysis of polysorbate 20 degradation in the format of a biopharmaceutical formulation and makes a comparison with several established methods of analysis. METHODS: Polysorbate 20 samples were degraded in a controlled environment utilizing the enzyme pancreatic lipase to generate degradants that included lauric acid and the sorbitan polyoxyethylene side chain. A new method was developed with sufficient sensitivity to analyze the degraded solutions. Lauric acid was derivatized with the fluorescent reagent 9-anthryldiazomethane to form 9-anthrylmethylethyl ester. The derivatized lauric acid was separated by reversed-phase chromatography and detected by fluorescence or UV spectroscopy. Three established methods utilized to measure polysorbate 20 were evaluated for their ability to detect degraded polysorbate 20. These methods were: (1) fluorescence analysis with N-phenyl-1-naphthylamine fluorescent dye; (2) UV spectroscopy with ammonium cobaltothiocyanate colorimetric reagent; and (3) nuclear magnetic resonance (NMR). RESULTS: Polysorbate 20 incubation with lipase resulted in degraded polysorbate 20 as determined by the derivatized lauric acid assay. The UV spectroscopy assay utilizing ammonium cobaltothiocyanate reagent was not able to detect the degradation of polysorbate 20 in the samples. The fluorescence method of analysis detected polysorbate 20 degradation as an approximate 50% decrease in micelles in comparison to standard nondegraded polysorbate 20 solutions. NMR analysis resulted in similar proton peak areas for both degraded and nondegraded polysorbate 20 samples. NMR spectra did contain minor differences between the samples. CONCLUSIONS: It is essential to choose the appropriate method of polysorbate 20 evaluation to assess the content, stability, and compatibility of a formulation. Current established methods to assess polysorbate 20 may overlook and do not necessarily monitor the potential degradation of this surfactant, which results in the formation of lauric acid. Because this type of degradation may occur in a formulation by an enzymatically active biopharmaceutical, a new method of analysis has been established.

Chemistry, Pharmaceutical↗

Characterization of PC12 cell proliferation and differentiation-stimulated by ECM adhesion proteins and neurotrophic factors.

Among the various elements which influence axonal outgrowth in vivo is the physicochemical interaction of actively outgrowing nerve fibers with the various substrata they encounter during differentiation. Several experiments have explored the role of the extracellular matrix (ECM) in the control of neuronal differentiation. The nature, however, of the interactions between neurons and components of the ECM during regeneration and development are largely a matter of speculation. Although previous studies have already explored the influence of a number of ECM adhesion proteins and neurotrophic factors on neurite outgrowth, none have been carried in a systematic approach that allows for the simultaneous comparison of different surface conditions in relation to different neurotrophic factors. Motivated by the necessity of establishing controlled environments that allow for the rational design of stable neuronal/biomaterial interfaces, the long-term effects of NGF and FGF-2 on the behavior of PC12 cells plated on collagen and laminin modified surfaces were evaluated. A pheochromocytoma cell line derived from transplantable rat adrenal medulla, PC12 cells have been commonly employed as an instructive model for studying the underlying mechanisms of neuronal differentiation. Long-term characterization of PC12 proliferation and neuronal differentiation for an experimental duration of 7-22 days was achieved by both qualitatively and quantitatively assaying for cell count, neurite number, neurite mean length, and neurite stability. Neurite stability was determined in terms of resistance to loss after neurotrophic factor (NGF/FGF-2) withdrawal. The present findings demonstrate that ECM adhesion proteins collagen and laminin are equally effective in promoting PC12 proliferation. It was noted as well that NGF supplemented collagen cultures are significantly more efficient in providing long-term support to PC12 differentiation in terms of neurite number, mean length, and stability.

Journal Article↗

Acclimation to temperature of the response of photosynthesis to increased carbon dioxide concentration in Taraxacum officinale.

The relative stimulation of photosynthesis by elevated carbon dioxide in C(3) species normally increases strongly with increasing temperature. This results from the kinetic characteristics of Rubisco, and has potentially important implications for responses of vegetation to increasing atmospheric carbon dioxide. It is often assumed that because Rubisco characteristics are conservative, all C(3) species have the same temperature dependence of the response of photosynthesis to elevated carbon dioxide. However, in this field study of Taraxacum officinale, there were no significant differences in the relative stimulation of photosynthesis by elevated carbon dioxide among days with temperatures ranging from 15 to 34 degrees C. Nevertheless, short-term measurements indicated a strong temperature dependence of the stimulation. This suggested that acclimation to temperature caused the lack of variation in the seasonal data. Experiments in controlled environments indicated that complete acclimation of the relative stimulation of photosynthesis by elevated carbon dioxide occurred for growth temperatures of 10 - 25 degrees C. The apparent specificity of Rubisco for carbon dioxide relative to oxygen at 15 degrees C, as assayed in vivo by measurements of the carbon dioxide concentration at which carboxylation equalled oxygenation, also varied with growth temperature. Changes in the apparent specificity of Rubisco accounted for the acclimation of the temperature dependence of the relative stimulation of photosynthesis by elevated carbon dioxide. It is premature to conclude that low temperatures will necessarily reduce the relative stimulation of photosynthesis caused by rising atmospheric carbon dioxide.

Journal Article↗

Adjustments of net photosynthesis in Solanum tuberosum in response to reciprocal changes in ambient and elevated growth CO2 partial pressures.

Single leaf photosynthetic rates and various leaf components of potato (Solanum tuberosum L.) were studied 1-3 days after reciprocally transferring plants between the ambient and elevated growth CO2 treatments. Plants were raised from individual tuber sections in controlled environment chambers at either ambient (36 Pa) or elevated (72 Pa) CO2. One half of the plants in each growth CO2 treatment were transferred to the opposite CO2 treatment 34 days after sowing (DAS). Net photosynthesis (Pn) rates and various leaf components were then measured 34, 35 and 37 DAS at both 36 and 72 Pa CO2. Three-day means of single leaf Pn rates, leaf starch, glucose, initial and total Rubisco activity, Rubisco protein, chlorophyll (a+b), chlorophyll (a/b), alpha-amino N, and nitrate levels differed significantly in the continuous ambient and elevated CO2 treatments. Acclimation of single leaf Pn rates was partially to completely reversed 3 days after elevated CO2-grown plants were shifted to ambient CO2, whereas there was little evidence of photosynthetic acclimation 3 days after ambient CO2-grown plants were shifted to elevated CO2. In a four-way comparison of the 36, 72, 36 to 72 (shifted up) and 72 to 36 (shifted down) Pa CO2 treatments 37 DAS, leaf starch, soluble carbohydrates, Rubisco protein and nitrate were the only photosynthetic factors that differed significantly. Simple and multiple regression analyses suggested that negative changes of Pn in response to growth CO2 treatment were most closely correlated with increased leaf starch levels.

Journal Article↗

Perception and sensitivity to horizontal turbulent air flows at the head region.

This work deals with experimental investigations on human reaction to local air movements of people in global thermal comfort, performing light activity. An analysis on draught risk was developed comparing the results with previous research findings on human response to draught. The intensity of air velocity, in terms of mean value and relative turbulence, was referred to the level at which normally clothed people could perceive and feel air movements behind the neck, in global neutral thermal condition. This work provides evidence of how the exposure duration to air movements plays a fundamental role on air flow sensitivity. The human reaction to an air flow was observed to vary with exposure duration: the feeling changes in intensity while the air flow persists blowing constantly. Moreover, different reactions have been observed between female and male test persons. Although these results were observed in the typical situation of horizontal air jet flows blowing from behind, they could apply in climatically controlled environments, where air flow is supplied horizontally at low speed, and the occupants are sitting far from the inlet section.

Adult↗

You can't always get what you want: educational attainment, agency, and choice.

Using educational attainment to indicate socioeconomic status, the authors examined models of agency and effects of choice among European American adults of different educational backgrounds in 3 studies. Whereas college-educated (BA) participants and their preferred cultural products (i.e., rock music lyrics) emphasized expressing uniqueness, controlling environments, and influencing others, less educated (HS) participants and their preferred cultural products (i.e., country music lyrics) emphasized maintaining integrity, adjusting selves, and resisting influence. Reflecting these models of agency, HS and BA participants differently responded to choice in dissonance and reactance paradigms: BA participants liked chosen objects more than unchosen objects, but choice did not affect HS participants' preferences. Results suggest that HS and BA models of agency qualitatively differ, despite overlap between HS and BA worlds.

Achievement↗

Astroglia induce neurogenesis from adult neural stem cells.

During an investigation of the mechanisms through which the local environment controls the fate specification of adult neural stem cells, we discovered that adult astrocytes from hippocampus are capable of regulating neurogenesis by instructing the stem cells to adopt a neuronal fate. This role in fate specification was unexpected because, during development, neurons are generated before most of the astrocytes. Our findings, together with recent reports that astrocytes regulate synapse formation and synaptic transmission, reinforce the emerging view that astrocytes have an active regulatory role--rather than merely supportive roles traditionally assigned to them--in the mature central nervous system.

Aging↗

Evidence for superfluidity of ultracold fermions in an optical lattice.

The study of superfluid fermion pairs in a periodic potential has important ramifications for understanding superconductivity in crystalline materials. By using cold atomic gases, various models of condensed matter can be studied in a highly controllable environment. Weakly repulsive fermions in an optical lattice could undergo d-wave pairing at low temperatures, a possible mechanism for high temperature superconductivity in the copper oxides. The lattice potential could also strongly increase the critical temperature for s-wave superfluidity. Recent experimental advances in bulk atomic gases include the observation of fermion-pair condensates and high-temperature superfluidity. Experiments with fermions and bosonic bound pairs in optical lattices have been reported but have not yet addressed superfluid behaviour. Here we report the observation of distinct interference peaks when a condensate of fermionic atom pairs is released from an optical lattice, implying long-range order (a property of a superfluid). Conceptually, this means that s-wave pairing and coherence of fermion pairs have now been established in a lattice potential, in which the transport of atoms occurs by quantum mechanical tunnelling and not by simple propagation. These observations were made for interactions on both sides of a Feshbach resonance. For larger lattice depths, the coherence was lost in a reversible manner, possibly as a result of a transition from superfluid to insulator. Such strongly interacting fermions in an optical lattice can be used to study a new class of hamiltonians with interband and atom-molecule couplings.

Journal Article↗