Release of non-exchangeable {}^{{{\text{15}}}}{\text{NH}}^{{\text{ + }}}_{{\text{4}}} from subgrade, decomposed granite substrates and uptake by non-mycorrhizal and mycorrhizal California native annual grass, Vulpia microstachys

Release rates of recently fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ from non-exchangeable interlayer sites in 2:1 silicate minerals were determined for decomposed granite (DG) saprolites from three locations in California, USA. Recently-fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ release from the DG substrate was quantified by extracting diffused $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ with H-resin, as well as a native, annual grass Vulpia microstachys. The $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ release data varied with via the method of extraction, which included H-resin pre-treatments (Na⁺ or H⁺) and V. microstachys uptake (mycorrhizal inoculated or uninoculated). After 6 weeks (1008 h), more $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ was recovered from fixed interlayer positions by the H-resins as compared to uptake by V. microstachys. The H⁺ treated H-resins recovered more released $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ (≈94 mg ${\text{NH}}^{{\text{ + }}}_{{\text{4}}} - {\text{N}}\;{\text{kg}}^{1} $ or (12%) of total fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ ) in two of the three DG samples as compared to the Na⁺ treated resins, (which recovered ≈70–78 mg ${\text{NH}}^{{\text{ + }}}_{{\text{4}}} - {\text{N}}\;{\text{kg}}^{{{\text{ - 1}}}} $ (or 9–10%) of the total fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ ). The V. microstachys assimilated 8–9% of the total fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ with mycorrhizal inoculum as compared to only 2% without a mycorrhizal inoculum, over the same time period. The fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ release kinetics from the H-resin experiments were most accurately described by first order and power function models, and can be characterized as biphasic using a heterogeneous diffusion model. Uptake of both the ¹⁵N and ambient, unlabelled N from the soils was closely related to plant biomass. There was no significant difference in percent of N per unit of biomass between the control and mycorrhizal treatments. The findings presented here indicate that observed, long-term $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ release rates from DG in studies utilizing resins, may overestimate the levels of fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ made available to plants and microorganisms. Additionally, the study suggested that mycorrhizae facilitate the acquisition and plant uptake of fixed $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ , resulting in markedly increased plant biomass production.     

<Superscript>1</Superscript>H, <Superscript>13</Superscript>C, <Superscript>15</Superscript>N resonance assignments of the extracellular loop 1 domain (ECL1) of <Emphasis Type="Italic">Streptococcus pneumoniae</Emphasis> D39 FtsX,an essential cell division protein

FtsX is an integral membrane protein from Streptococcus pneumoniae (pneumococcus) that harbors an extracellular loop 1 domain (\({\text{FtsX}}^{\text{ECL1}}_{Spn}\)) that interacts with PcsB, an peptidoglycan hydrolase that is essential for cell growth and division. Here, we report nearly complete backbone and side chain resonance assignments and a secondary structural analysis of \({\text{FtsX}}^{\text{ECL1}}_{Spn}\) (residues 47–168 of FtsX) as first steps toward structure determination of \({\text{FtsX}}^{\text{ECL1}}_{Spn}\).     

A comparative study of the mechanism of Na+ and Cl? excretion by the gill ofMugil capito andFundulus heteroclitus: Effects of Stress

Summary In seawater (SW)-adaptedMugil andFundulus, gill effluxes of Na⁺ and of Cl^– and the simultaneously recorded transgill potential (P.D.) differ according to whether they are measured in stressed or rested animals.In rested animals of the two species, transfer to Ringer's solution considerably reduces the P.D. but not . InFundulus, is also decreased. Transfer of the two species from SW to fresh water (FW) reduces and by 75 to 85% and leads to a large inversion of P.D. When K⁺ is added to FW, a gill depolarization occurs, as well as a large increase of and .These results suggest that: 1) the P.D. originates primarily from the diffusion of cations, the gill permeability to Na⁺ ( ) being greater than that to Cl^– ( ), 2) a Cl^–/Cl^– exchange independent of P.D. is associated with the Cl^– pump; 3) Cl^– pump activity is linked to Na⁺/K⁺ exchange which in turn is associated to a Na⁺/Na⁺ exchange diffusion mechanism.In stressed individuals of the two species, the P.D. in SW, as well as the P.D. changes observed during transfer experiments, are considerably reduced. The decrease of and observed after transfer from SW to FW are also minimised. Changes are smaller inFundulus. The decrease of P.D. characterizing stressed animals may be at least in part due to a 3 to 4 fold increase of which becomes equal to in both species.As a result of stress, the K⁺-activated Na⁺ and Cl^– excretion mechanisms are totally inhibited inFundulus and partially so inMugil.Stress response seems more intense inFundulus and recovery from stress faster inMugil.     

Growth yields and saturation constant of Desulfovibrio vulgaris in chemostat culture

Desulfovibrio vulgaris (strain Marburg) was grown on H₂ and sulfate as sole energy source in a chemostat limited by the sulfate supply. The biomass concentration and the sulfate concentration in the culture were determined as a function of the dilution rate. From the data a K _S (saturation constant) for sulfate of 10 M, a _max of 0.23 h^–1, and a of 13 g/mol were calculated. The organism was also grown in chemostat culture on H₂ and sulfite, H₂ and thiosulfate, and pyruvate (without sulfate). was found to be 35 g/mol, 36 g/mol, and Y _pyr ^max 10 g/mol. The growth yields are discussed with respect to ATP gains in dissimilatory sulfate reduction.     

Interaction-induced electric (hyper)polarizability in the dihydrogen–neon pair: basis set and electron correlation effects

We investigated the interaction (hyper)polarizability of neon–dihydrogen pairs by performing high-level ab initio calculations with atom/molecule-specific, purpose-oriented Gaussian basis sets. We obtained interaction-induced electric properties at the SCF, MP2, and CCSD levels of theory. At the CCSD level, for the T-shaped configuration, around the respective potential minimum of 6.437 a₀, the interaction-induced mean first hyperpolarizability varies for 5?<? R/a₀?<?10 as

$$ \left[{\overline{\beta}}_{\mathrm{int}}(R)\hbox{-} {\overline{\beta}}_{\mathrm{int}}\left({R}_{\mathrm{e}}\right)\right]/{e}^3{a_0}^3{E_{\mathrm{h}}}^{-2}=-0.91\left(R\hbox{-} {R}_{\mathrm{e}}\right)+0.50{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^2\hbox{--} 0.13{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^3+0.01{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^4. $$

Again, at the CCSD level, but for the L-shaped configuration around the respective potential minimum of 6.572 a₀, this property varies for 5?<? R/a₀?<?10 as

$$ \left[{\overline{\beta}}_{\mathrm{int}}(R)\hbox{-} {\overline{\beta}}_{\mathrm{int}}\left({R}_{\mathrm{e}}\right)\right]/{e}^3{a_0}^3{E_{\mathrm{h}}}^{-2}=-1.33\left(R\hbox{-} {R}_{\mathrm{e}}\right)+0.75{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^2-0.20{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^3+0.02{\left(R\hbox{-} {R}_{\mathrm{e}}\right)}^4. $$

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Graphical Abstract Interaction-induced mean dipole polarizability (\( \overline{a} \)) for the T-shaped configuration of H₂–Ne calculated at the SCF, MP2, and CCSD levels of theory

     

Factors affecting denitrification in agricultural headwater streams in Northeast Ohio,USA

As a result of increased anthropogenic nitrogen (N) loading in surface waters of agricultural watersheds, there is enhanced interest to understand and quantify N removal mechanisms. Denitrification, an important N removal mechanism in aquatic systems, may contribute to reducing N pollution in agricultural headwater streams. However, the key factors controlling this process in lotic systems remain unclear. The objective of our study was to examine the factors regulating rates of denitrification in the sediments of agricultural headwater streams in the mid-western USA. Denitrification rates were variable among streams and treatments (<0.1–28.0 μg N g AFDM⁻¹ h⁻¹) and on average, were higher than those reported for similar headwater streams. Carbon quantity and quality, and pH had no effect on denitrification, while temperature and nitrate ( ) concentrations had a positive effect on rates of denitrification. Specifically, controlled denitrification following Michaelis-Menten kinetics. We calculated a value of k_m (1.0 mg -N L^-1) that was comparable to other studies in aquatic sediments but was well below the median in-stream concentrations (5.2–17.4 mg -N L⁻¹) observed at the study sites. Despite high rates of denitrification, this removal mechanism is most likely saturated in the agricultural headwater streams we examined, suggesting that these systems are not effective at removing in-stream N. Handling editor: D. Ryder     

(H)NCAHA and (H)CANNH experiments for the determination of vicinal coupling constants related to the ϕ-torsion angle

Summary A set of three-dimensional triple-resonance experiments is described which provide , , and coupling constants. The pulse sequences generate E.COSY-like multiplet patterns and comprise a magnetization transfer from the amide proton to the α-proton or vice versa via the directly bound heteronuclei. For residues with the ¹H^α spin resonating close to the H₂O signal, a modified HNCA experiment can be employed to measure the vicinal ¹H^N,¹H^α couplings. Ambiguities associated with the conversion of values into ϕ-angle constraints for protein structure determination can be resolved with the knowledge of the heteronuclear ³J-couplings. In favourable cases, stereospecific assignments of glycine α-protons can be obtained by employing the experiments described here in combination with NOE data. The methods are applied to flavodoxin from Desulfovibrio vulgaris.     

Energy requirements of Adélie penguin (Pygoscelis adeliae) chicks

Summary The energy requirements of Adélie penguin (Pygoscelis adeliae) chicks were analysed with respect to body mass (W, 0.145–3.35 kg, n=36) and various forms of activity (lying, standing, minor activity, locomotion, walking on a treadmill). Direct respirometry was used to measure O₂ consumption ( ) and CO₂ production. Heart rate (HR, bpm) was recorded from the ECG obtained by both externally attached electrodes and implantable HR-transmitters. The parameters measured were not affected by hand-rearing of the chicks or by implanting transmitters. HR measured in the laboratory and in the field were comparable. Oxygen uptake ranged from in lying chicks to at maximal activity, RQ=0.76. Metabolic rate in small wild chicks (0.14–0.38 kg) was not affected by time of day, nor was their feeding frequency in the colony (Dec 20–21). Regressions of HR on were highly significant (p< 0.0001) in transmitter implanted chicks (n=4), and two relationships are proposed for the pooled data, one for minor activities ( ), and one for walking ( ). Oxygen consumption, mass of the chick (2–3 kg), and duration of walking (T, s) were related as , whereas mass-specific O₂ consumption was related to walking speed (S, m·s^-1) as .Abbreviations bpm beats per minute - D distance walked (m) - ECG electrocardiogram - HR heart rate (bpm) - ns number of steps - RQ respiratory quotient - S walking speed (m·s^-1) - T time walked (s) - W body mass (kg)     

Measurement of eight scalar and dipolar couplings for methine–methylene pairs in proteins and nucleic acids

A new 3D, spin-state-selective coherence transfer NMR experiment is described that yields accurate measurements for eight scalar or dipolar couplings within a spin system composed of a methylene adjacent to a methine group. Implementations of the experiment have been optimized for proteins and for nucleic acids. The experiments are demonstrated for C–C moieties of the third IgG-binding domain from Streptococcal Protein G (GB3) and for C –C groups in a 24-nt RNA oligomer. Chemical shifts of C, C and H (respectively C , C and H ) are dispersed in the three orthogonal dimensions, and the absence of heteronuclear decoupling leads to distinct and well-resolved E.COSY multiplet patterns. In an isotropic sample, the E.COSY displacements correspond to ¹J_CH, ²J_CH2+²J_CH3, ²J_CH, ¹J_CH2+¹J_CH3, ¹J_CH2–²J_H2H3, ¹J_CH3–²J_H2H3, ³J_HH2 and ³J_HH3 for proteins, and ¹J , ²J J , ²J , ¹J +¹J , ¹J J , ¹J J , ³J and ³J in nucleic acids. The experiment, based on relaxation-optimized spectroscopy, yields best results when applied to residues where the methine–methylene group corresponds to a reasonably isolated spin system, as applies for C, F, Y, W, D, N and H residues in proteins, or the C –C groups in nucleic acids. Splittings can be measured under either isotropic or weakly aligned conditions, yielding valuable structural information both through the ³J couplings and the one-, two- and three-bond dipolar interactions. Dipolar couplings for 10 out of 13 sidechains in GB3 are found to be in excellent agreement with its X-ray structure, whereas one residue adopts a different backbone geometry, and two residues are subject to extensive ₁ rotamer averaging. The abundance of dipolar couplings can also yield stereospecific assignments of the non-equivalent methylene protons. For the RNA oligomer, dipolar data yielded stereospecific assignments for six out of the eight C H₂ groups in the loop region of the oligomer, in all cases confirmed by ¹J ^{1} $$" align="middle" border="0"> J , and H resonating downfield of H .Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s10858-005-0175-z.     

Retention of Dissolved Inorganic Nitrogen by Foliage and Twigs of Four Temperate Tree Species

Nitrogen (N) retention by tree canopies is believed to be an important process for tree nutrient uptake, and its quantification is a key issue in determining the impact of atmospheric N deposition on forest ecosystems. Due to dry deposition and retention by other canopy elements, the actual uptake and assimilation by the tree canopy is often obscured in throughfall studies. In this study, ¹⁵N-labeled solutions ( $ ^{15} {\text{NH}}_{4}^{ + } $ and $ ^{15} {\text{NO}}_{3}^{ - } $ ) were used to assess dissolved inorganic N retention by leaves/needles and twigs of European beech, pedunculate oak, silver birch, and Scots pine saplings. The effects of N form, tree species, leaf phenology, and applied $ {\text{NO}}_{3}^{ - } $ to $ {\text{NH}}_{4}^{ + } $ ratio on the N retention were assessed. Retention patterns were mainly determined by foliar uptake, except for Scots pine. In twigs, a small but significant ¹⁵N enrichment was detected for $ {\text{NH}}_{4}^{ + } $ , which was found to be mainly due to physicochemical adsorption to the woody plant surface. The mean $ {{^{15} {\text{NH}}_{4}^{ + } } \mathord{\left/ {\vphantom {{^{15} {\text{NH}}_{4}^{ + } } {^{15} {\text{NO}}_{3}^{ - } }}} \right. \kern-0em} {^{15} {\text{NO}}_{3}^{ - } }} $ retention ratio varied considerably among species and phenological stadia, which indicates that the use of a fixed ratio in the canopy budget model could lead to an over- or underestimation of the total N retention. In addition, throughfall water under each branch was collected and analyzed for $ ^{15} {\text{NH}}_{4}^{ + } $ , $ ^{15} {\text{NO}}_{3}^{ - } $ , and all major ions. Net throughfall of $ ^{15} {\text{NH}}_{4}^{ + } $ was, on average, 20 times higher than the actual retention of $ ^{15} {\text{NH}}_{4}^{ + } $ by the plant material. This difference in $ ^{15} {\text{NH}}_{4}^{ + } $ retention could not be attributed to pools and fluxes measured in this study. The retention of $ ^{15} {\text{NH}}_{4}^{ + } $ was correlated with the net throughfall of K⁺, Mg²⁺, Ca²⁺, and weak acids during leaf development and the fully leafed period, while no significant relationships were found for $ ^{15} {\text{NO}}_{3}^{ - } $ retention. This suggests that the main driving factors for $ {\text{NH}}_{4}^{ + } $ retention might be ion exchange processes during the start and middle of the growing season and passive diffusion at leaf senescence. Actual assimilation or abiotic uptake of N through leaves and twigs was small in this study, for example, 1–5% of the applied dissolved ¹⁵N, indicating that the impact of canopy N retention from wet deposition on forest productivity and carbon sequestration is likely limited.     

Concentration-Dependent Effects on Intracellular and Surface pH of Exposing <Emphasis Type="Italic">Xenopus</Emphasis> oocytes to Solutions Containing NH<Subscript>3</Subscript>/NH<Subscript>4</Subscript><Superscript>+</Superscript>

Others have shown that exposing oocytes to high levels of (10–20 mM) causes a paradoxical fall in intracellular pH (pH_i), whereas low levels (e.g., 0.5 mM) cause little pH_i change. Here we monitored pH_i and extracellular surface pH (pH_S) while exposing oocytes to 5 or 0.5 mM NH₃/NH₄ ⁺. We confirm that 5 mM causes a paradoxical pH_i fall (−ΔpH_i ≅ 0.2), but also observe an abrupt pH_S fall (−ΔpH_S ≅ 0.2)—indicative of NH₃ influx—followed by a slow decay. Reducing [NH₃/NH₄ ⁺] to 0.5 mM minimizes pH_i changes but maintains pH_S changes at a reduced magnitude. Expressing AmtB (bacterial Rh homologue) exaggerates −ΔpH_S at both levels. During removal of 0.5 or 5 mM NH₃/NH₄ ⁺, failure of pH_S to markedly overshoot bulk extracellular pH implies little NH₃ efflux and, thus, little free cytosolic NH₃/NH₄ ⁺. A new analysis of the effects of NH₃ vs. NH₄ ⁺ fluxes on pH_S and pH_i indicates that (a) NH₃ rather than NH₄ ⁺ fluxes dominate pH_i and pH_S changes and (b) oocytes dispose of most incoming NH₃. NMR studies of oocytes exposed to ¹⁵N-labeled show no significant formation of glutamine but substantial accumulation in what is likely an acid intracellular compartment. In conclusion, parallel measurements of pH_i and pH_S demonstrate that NH₃ flows across the plasma membrane and provide new insights into how a protein molecule in the plasma membrane—AmtB—enhances the flux of a gas across a biological membrane.

Adiabatic transformability hypothesis of human locomotion

It is hypothesized that metabolic and mechanical changes in human locomotion associated with changes in speed v are constrained by two attractive strategies: $Q_{{\text{metab}}} = 1{\text{ and }}\Delta Q_{{\text{metab}}} /\Delta v = {\text{a}}$ positive definite constant. $Q_{{\text{metab}}} = \Delta {\rm E}_{\text{k}} {\text{s}}^{{\text{ - 1}}} /{\text{ml O}}_{\text{2}} {\text{s}}^{{\text{ - 1}}} $ where ΔEs^?1 is the summed increments and decrements per unit time in the translational and rotational kinetic energies of the body's segments and ml O₂s^?1 is the rate at which chemical energy is dissipated. The expected constancy of ΔQ _metab/Δv _metab was derived from an extension of Ehrenfest's adiabatic hypothesis by which transformations (increases, decreases) in locomotion v can be considered as adiabatic, even though the biological conditions are nonconservative and non-rate-limited. The expected significance of Q _metab=1 was derived from stability considerations of the symmetry per stride of stored and dissipated energy. An experimental evaluation was provided by collecting metabolic and mechanical measures on walking (10 subjects) and running (9 subjects) at progressively greater treadmill speeds but within the aerobic limit. Results revealed that walking was restricted to ometab ? 1 with a nonlinear trajectory in v×Q _metab coordinates shaped by Q _metab=1 (primarily) and the constancy of ΔQ _metab/Δv. Running satisfied Q _metab > 1, with a linear trajectory in v×Q _metab coordinates conforming to ΔQ _metab/_Δv=a constant, with the constant predicted from invariants in the mechanical space v×ΔE _ks^?1. Results also suggested that the metabolic costs of running might be predictable from measures made in the v×ΔE _ks^?1 space.     

Nitrogen metabolism of asparagine and glutamate in Vero cells studied by <Superscript>1</Superscript>H/<Superscript>15</Superscript>N NMR spectroscopy

Glutamine-free culture of Vero cells has previously been shown to cause higher cell yield and lower ammonia accumulation than that in glutamine-containing culture. Nitrogen metabolism of asparagine and glutamate as glutamine replacer was studied here using nuclear magnetic resonance (NMR) spectroscopy. ¹⁵N-labelled glutamate or asparagine was added and their incorporation into nitrogenous metabolites was monitored by heteronuclear multiple bond coherence (HMBC) NMR spectroscopy. In cells incubated with l-[¹⁵N]glutamate, the ¹⁵N label was subsequently found in a number of metabolites including alanine, aspartate, proline, and an unidentified compound. No detectable signal occurred, indicating that glutamate was utilized by transamination rather than by oxidative deamination. In cells incubated with l-[2-¹⁵N]asparagine, the ¹⁵N label was subsequently found in aspartate, the amine group of glutamate/glutamine, and in two unidentified compounds. Incubation of cells with l-[4-¹⁵N]asparagine showed that the amide nitrogen of asparagine was predominantly transferred to glutamine amide. There was no detectable production of , showing that most of the asparagine amide was transaminated by asparagine synthetase rather than deaminated by asparaginase. Comparing with a glutamine-containing culture, the activities of phosphate-activated glutaminase (PAG), glutamate dehydrogenase (GDH) and alanine aminotransferase (ALT) decreased significantly and the activity of aspartate aminotransferase (AST) decreased slightly.     

Determination of heteronuclear three-bond J-coupling constants in peptides by a simple heteronuclear relayed E.COSY experiment

Summary A simple heteronuclear relayed E.COSY pulse sequence with a minimum number of pulses is proposed for the quantitative determination of heteronuclear three-bond J-coupling constants in uniformly ¹³C-enriched polypeptide samples. Numerous heteronuclear three-bond coupling constants, including , , , and , can be determined for each residue from a single heteronuclear relayed E.COSY spectrum. Couplings relevant for stereospecific assignments as well as for the determination of dihedral angles in the amino acid backbone and in side chains are obtained. The method is demonstrated on the uniformly ¹³C-enriched decapeptide antamanide (-Val¹-Pro²-Pro³-Ala⁴-Phe⁵-Phe⁶-Pro⁷-Pro⁸-Phe⁹-Phe¹⁰-).     

Bioaccumulation of Heavy Metals by Green Algae

The biosorption of metal ions (Cr⁺³, , Cu⁺², and Ni⁺²) on two algal blooms (designated HD-103 and HD-104) collected locally was investigated as a function of the initial metal ion concentration. The main constituent of HD-103 is Cladophora sp., while Spirulina sp. is present significantly in the bloom HD-104. Algal biomass HD-103 exhibited the highest Cu⁺² uptake capacity (819 mg/g). This bloom adsorbed Ni⁺² (504 mg/g), Cr⁺³ (347 mg/g), and (168 mg/g). Maximum of Ni⁺² (1108 mg/g) is taken by HD-104. This species takes up 306, 202, and 576 mg/g Cr⁺³, , and Cu⁺², respectively. Equilibrium data fit very well to both the Langmuir and the Freundlich isotherm models. The sorption process followed the Freundlich model better. Pseudo-first-order kinetic model could describe the kinetic data. Infrared (IR) spectroscopic data were employed to identify the site(s) of bonding. It was found that phosphate and peptide moieties participate in the metal uptake by bloom HD-103. In the case of bloom HD-104, carboxylate and phosphate are responsible for the metal uptake. The role of protein in metal uptake by HD-103 was investigated using polyacrylamide gel electrophoresis.     

Transition from octahedral to tetrahedral geometry causes the activation or inhibition by Zn<Superscript>2+</Superscript> of <Emphasis Type="Italic">Pseudomonas aeruginosa</Emphasis> phosphorylcholine phosphatase

Pseudomonas aeruginosa phosphorylcholine phosphatase (PchP) catalyzes the hydrolysis of phosphorylcholine, which is produced by the action of hemolytic phospholipase C on phosphatidylcholine or sphyngomielin, to generate choline and inorganic phosphate. Among divalent cations, its activity is dependent on Mg²⁺ or Zn²⁺. Mg²⁺ produced identical activation at pH 5.0 and 7.4, but Zn²⁺ was an activator at pH 5.0 and became an inhibitor at pH 7.4. At this higher pH, very low concentrations of Zn²⁺ inhibited enzymatic activity even in the presence of saturating Mg²⁺ concentrations. Considering experimental and theoretical physicochemical calculations performed by different authors, we conclude that at pH 5.0, Mg²⁺ and Zn²⁺ are hexacoordinated in an octahedral arrangement in the PchP active site. At pH 7.4, Mg²⁺ conserves the octahedral coordination maintaining enzymatic activity. The inhibition produced by Zn²⁺ at 7.4 is interpreted as a change from octahedral to tetrahedral coordination geometry which is produced by hydrolysis of the [ \textZn ²⁺ \textL ₂ ^{- 1} \textL ₂⁰ ( \textH ₂ \textO ) ₂ ] \left[ {{\text{Zn}}^{ 2+ } {\text{L}}_{ 2}^{ - 1} {\text{L}}_{ 2}^{0} \left( {{\text{H}}_{ 2} {\text{O}}} \right)_{ 2} } \right] complex.     

Effects of common soil anions and pH on the uptake and accumulation of perchlorate in lettuce

A mechanistic understanding of perchlorate () entry into plants is important for establishing the human health risk associated with consumption of contaminated produce and for assessing the effectiveness of phytoremediation. To determine whether common soil anions affect uptake and accumulation in higher plants, a series of competition experiments using lettuce (Lactuca sativa L.) were conducted between (50 nM) and (4–12 mM), (1–10 mM), or Cl⁻ (5–15 mM) in hydroponic solution. The effects of (0–5 mM) and pH (5.5–7.5) on uptake were also examined. Increasing in solution significantly reduced the amount of taken up by green leaf, butter head, and crisphead lettuces. Sulfate and Cl⁻ had no significant effects on uptake in lettuce over the concentrations tested. Increasing pH significantly reduced the amount of taken up by crisphead and green leaf lettuces, whereas increasing significantly reduced uptake in butter head lettuce. The inhibition by across all lettuce genotypes suggests that may share an ion carrier with , and the decrease in uptake with increasing pH or provides macroscopic evidence for cotransport across the plasma membrane.     

Topography of nucleic acid helices in solutions. 3. Interactions of spermine and spermidine derivatives with polyadenylic-polyuridylic and polyinosinic-polycytidylic acid helices

The synthesis of spermine derivatives (II), \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}_1 {\rm R}_{\rm 2} {\rm R}_{\rm 3} \mathop {\rm N}\limits^ + \left( {{\rm CH}_2 } \right)_3 \mathop {\rm N}\limits^ + {\rm R}_{\rm 1} {\rm R}_{\rm 2} \left( {{\rm CH}_2 } \right)_2 ]_2 \cdot 4{\rm X}^ - $\end{document}, and spermidine derivatives (III), \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}_1 {\rm R}_{\rm 2} {\rm R}_{\rm 3} \mathop {\rm N}\limits^ + \left( {{\rm CH}_2 } \right)_4 \mathop {\rm N}\limits^ + {\rm R}_{\rm 1} {\rm R}_{\rm 2} \left( {{\rm CH}_2 } \right)_3 \mathop {\rm N}\limits^ + {\rm R}_{\rm 1} {\rm R}_{\rm 2} {\rm R}_3 \cdot 3{\rm X}^ - $\end{document}, are reported. The effects of these salts on the helix–coil transition of rA–rU and rI–rC helices were examined. Increasing the size of the hydrophobic substituents, R¹, R², and R³ lowers the degree of stabilization of the helical structure. The disproportionation reaction, 2rA–rU→rA–rU₂ + rA occurs readily with salts II and III, especially when the substituents, R₁, R₂, and R₃ are small, i.e., H or Me. Spermine is found to stabilize the rA–rU² and rI–rC helices to approximately the same extent; however, large differences between the degree of stabilization of rA–rU₂ and rI-rC helices are observed when the substituents R₁, R₂, and R₃ are large hydrophobic groups. Similar results are also obtained for the spermidine series. Finally, differences in the interactions of the salts II and III with rA–rU₂ and rI–rC helices suggest that the latter helix is denser.     

Three years of soil respiration in a mature eucalypt woodland exposed to atmospheric CO<Subscript>2</Subscript> enrichment

Large amounts of atmospheric N deposition cause negative effects on ecosystems. Effective mitigation strategies require the sources of N deposition to be identified and the contributions from individual sources to be quantified. Determination of the isotopic composition represents a useful approach in source apportionment. In this study, the δ¹⁵N-NH_x of wet and dry atmospheric deposition and the main NH₃ emission sources were analyzed at an urban, a suburban and a rural site in the Taihu Lake region of China. The 2-year average δ¹⁵N-\( {\text{NH}}_{4}^{ + } \) of precipitation was ? 3.0 ± 2.3, ? 3.1 ± 2.8 and ? 0.5 ± 2.8‰ for the urban, suburban and rural sites, respectively. These values were much lower than the corresponding values for particulate \( {\text{NH}}_{4}^{ + } \) (15.9, 15.2 and 14.3‰ at the urban, suburban and rural sites, respectively), and much higher than those of gaseous δ¹⁵N-NH₃ (? 16.7, ? 18.2 and ? 17.4‰ at the urban, suburban and rural sites, respectively). The δ¹⁵N-NH₃ of NH₃ from the main emission sources ranged from ? 30.8 to ? 3.3‰ for volatilized fertilizer, from ? 35.1 to ? 10.5‰ for emissions from a pig farm, and ? 24.7 to ? 11.3‰ for emissions from a dairy farm. Temporal variations of deposition δ¹⁵N-NH_x indicated that δ¹⁵N-NH_x values were lower in summer and autumn, but higher in winter and spring for both precipitation \( {\text{NH}}_{4}^{ + } \)-N and gaseous NH₃-N. Weather conditions such as temperature and precipitation significantly influenced the spatial and temporal distribution of isotope values of the deposition. Analysis of δ¹⁵N-NH_x in deposition and emission sources identified volatilized fertilizer and livestock wastes as the origins of both gaseous NH₃-N and precipitation \( {\text{NH}}_{4}^{ + } \)-N over the region. A stable isotope mixing model estimated that volatilized fertilizer and animal excreta contributed more than 65% to precipitation \( {\text{NH}}_{4}^{ + } \)-N, more than 60% to particulate \( {\text{NH}}_{4}^{ + } \)-N, and more than 75% to gaseous NH₃-N.