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Development and demonstration of reliable measurement techniques that can detect and help quantify the nature and extent of elemental mercury (Hg(0)) in the subsurface are needed to reduce uncertainties in the decision-making process and increase the effectiveness of remedial actions. We conducted field tests at the Y-12 National Security Complex in Oak Ridge, Tennessee, USA, to determine if sampling and analysis of Hg(0) vapors in the shallow subsurface (< 0.3 m depth) can be used to as an indicator of the location and extent of Hg(0) releases in the subsurface. We constructed a rigid polyvinyl chloride push probe assembly, which was driven into the ground. Soil gas samples were collected through a sealed inner tube of the assembly and were analyzed immediately in the field with a Lumex and/or Jerome Hg(0) analyzer. Time-series sampling showed that Hg vapor concentrations were fairly stable over time, suggesting that the vapor phase Hg(0) was not being depleted and that sampling results were not sensitive to the soil gas purge volume. Hg(0) vapor data collected at over 200 push probe locations at 3 different release sites correlated very well to areas of known Hg(0) contamination. Vertical profiling of Hg(0) vapor concentrations conducted at two locations provided information on the vertical distribution of Hg(0) contamination in the subsurface. We conclude from our studies that soil gas sampling and analysis can be conducted rapidly and inexpensively at large scales to help identify areas contaminated with Hg(0).

The X-ray crystal structure of Shewanella oneidensis OmcA, an extracellular decaheme cytochrome involved in mineral reduction, was solved to a resolution of 2.7Å. The four OmcA molecules in the asymmetric unit are arranged so the minimum distance between heme 5 on adjacent OmcA monomers is 9Å, indicative of a transient OmcA dimer capable of intermolecular electron transfer. A previously identified hematite binding motif was identified near heme 10, forming a hydroxylated surface that would bring a heme 10 electron egress site to ∼10Å of a mineral surface.

The hgcA and hgcB gene pair is essential for mercury (Hg) methylation by certain anaerobic bacteria, but little is known about how deletion of hgcAB affects the cell surface interactions and intracellular uptake of Hg. Here, we compare ΔhgcAB mutants with the wild-type (WT) strains of both Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132 and observe differences in Hg redox transformations, adsorption, and uptake in laboratory incubation studies. In both strains, deletion of hgcAB increased the rate of reduction of Hg(II) but decreased the rate of oxidation of Hg(0) under anaerobic conditions. The measured cellular thiol content in ΔhgcAB mutants was lower than that in the WT, accounting for the decreased rates of adsorption and uptake of Hg. Despite the lack of methylation activity, uptake of Hg by the ΔhgcAB mutant continued, albeit at a rate slower than that of the WT. These findings demonstrate that deletion of the hgcAB gene pair not only eliminates Hg methylation but also alters cel...

Organic thiols (R-SH) are known to react and form complexes with some toxic soft metals such as mercury (Hg) in both biotic and abiotic systems. However, a clear understanding of these interactions is currently limited because quantifying thiols in environmental matrices is difficult due to their low abundance, susceptibility to oxidation, and measurement interference by non-thiol compounds in samples. Here, we report a fluorescence-labeling method using a maleimide containing probe, ThioGlo-1 (TG-1), to determine total thiols directly on bacterial cells and natural organic matter (NOM). We systematically evaluated the optimal thiol labeling conditions and interference from organic compounds such as disulfide, methionine, thiourea, and amine, and inorganic ions such as Na(+), K(+), Ca(2+), Fe(2+), Cl(-), SO4(2-), HCO3(-), and SCN(-), and found that the method is highly sensitive and selective. Only relatively high levels of sulfide (S(2-)) and sulfite (SO3(2-)) significantly interfere with the thiol analysis. The method was successful in determining thiols in a bacterium Geobacter sulfurreducens PCA and its mutants in a phosphate buffered saline solution. The measured value of ~2.1 × 10(4) thiols cell(-1) (or ~0.07 µmol g(-1) wet cells) is in good agreement with that observed during reactions between Hg and PCA cells. Using the standard addition, we determined the total thiols of two reference NOM samples, the reduced Elliot soil humic acid and Suwanee River NOM, to be 3.6 and 0.7 µmol g(-1), respectively, consistent with those obtained based on their reactions with Hg.

Molecular-scale protein-mineral interactions are central to understanding electron transfer mechanisms and microbial processes in subsurface environments. Although, the electron transfer between c-type cytochrome and hematite has been investigated many factors impacting the electron transfer rate have not been determined. We investigated the interactions of horse heart cytochrome c (cyt c) with hematite nanowire array electrodes by cyclic voltammetry to study the electron transfer between redox active proteins and mineral surfaces. Using this model system, specific interactions of cyt c with hematite as a function of electrical potential and pH were examined. We observed direct electron transfer between cyt c and hematite with an interfacial electron transfer rate of kº ET = 0.6 s-1. show buffer pH has an apparent effect on the conformational and adsorption-induced change on the cyt c. Moreover, in the presence of the electron shuttling compound, anthraquinone-2,6-disulfonate (AQDS), electron transfer rate between cyt c and hematite increased to kº ET = 2 s-1, which is more than three times of the rate determined in absence of AQDS. This study provides into biomolecular factors controlling the complex interactions and electron transfer processes between redox-active proteins and minerals, which has broader implications for describing chemical transformations at biological-mineral interfaces at the molecular scale.

Methylmercury is a neurotoxin that poses significant health risks to humans. Laboratory experiments suggest that the activity of methylating and non-methylating bacteria may together enhance the formation of methylmercury in anaerobic environments.

Self-assembly behavior of an ABC triblock copolymer, poly(ethylene glycol)-b-polystyrene-b-poly(ε-caprolactone) (PEG-b-PS-b-PCL), in aqueous media is presented. The formed micelle structures were analyzed by using transmission electron microscopy, scanning electron microscopy, and laser light scattering. Various fascinating multicompartmental aggregates, including multilamellar vesicles, cylinder-containing vesicles, entrapped vesicles, and porous large compound micelles, were prepared from four copolymers with various block lengths of PEG and PS. The phase separation of hydrophobic PS and PCL blocks, as well as the hydrophilic/hydrophobic balance, plays a crucial role on the self-assembly behaviors. The mechanism regarding the formation of these fascinating aggregates is also suggested.

The frustrated Lewis pair tBu3P/B(C6F5)3 (1) readily adds SO2 to yield the zwitterionic adduct tBu3P+–S(O)–OB−(C6F5)3 (3). A series of intramolecular vicinal P/B FLPs Mes2P–(X)–B(C6F5)2 [X = –CH2–CH2– (2a), –CHMe–CH2– (2b), cyclo-C6H10 (5)] add SO2 at −78 °C to yield the corresponding six-membered addition products 4a, 4b, 6. The adducts contain a chiral sulfur center. The [B]–O–(O)S–[P] addition products 3, 4b and 6 were characterized by X-ray diffraction.

Understanding aqueous phase processes involving group 12 metal cations is relevant to both environmental and biological sciences. Here, quantum chemical methods and polarizable continuum models are used to compute the hydration free energies of a series of divalent group 12 metal cations (Zn(2+), Cd(2+), and Hg(2+)) together with Cu(2+) and the anions OH(-), SH(-), Cl(-), and F(-). A cluster-continuum method is employed, in which gas-phase clusters of the ion and explicit solvent molecules are immersed in a dielectric continuum. Two approaches to define the size of the solute-water cluster are compared, in which the number of explicit waters used is either held constant or determined variationally as that of the most favorable hydration free energy. Results obtained with various polarizable continuum models are also presented. Each leg of the relevant thermodynamic cycle is analyzed in detail to determine how different terms contribute to the observed mean signed error (MSE) and the standard deviation of the error (STDEV) between theory and experiment. The use of a constant number of water molecules for each set of ions is found to lead to predicted relative trends that benefit from error cancellation. Overall, the best results are obtained with MP2 and the Solvent Model D polarizable continuum model (SMD), with eight explicit water molecules for anions and 10 for the metal cations, yielding a STDEV of 2.3 kcal mol(-1) and MSE of 0.9 kcal mol(-1) between theoretical and experimental hydration free energies, which range from -72.4 kcal mol(-1) for SH(-) to -505.9 kcal mol(-1) for Cu(2+). Using B3PW91 with DFT-D3 dispersion corrections (B3PW91-D) and SMD yields a STDEV of 3.3 kcal mol(-1) and MSE of 1.6 kcal mol(-1), to which adding MP2 corrections from smaller divalent metal cation water molecule clusters yields very good agreement with the full MP2 results. Using B3PW91-D and SMD, with two explicit water molecules for anions and six for divalent metal cations, also yields reasonable agreement with experimental values, due in part to fortuitous error cancellation associated with the metal cations. Overall, the results indicate that the careful application of quantum chemical cluster-continuum methods provides valuable insight into aqueous ionic processes that depend on both local and long-range electrostatic interactions with the solvent.

Benzoic acid (BA) derivatives of environmental relevance exhibit various photophysical and photochemical characteristics. Here, time-dependent density functional theory (TDDFT) is used to calculate photoexcitations of eight selected BAs and the results are compared with UV spectra determined experimentally. High-level gas-phase EOM-CCSD calculations and experimental aqueous-phase spectra were used as the references for the gas-phase and aqueous-phase TDDFT results, respectively. A cluster-continuum model was used in the aqueous-phase calculations. Among the 15 exchange-correlation (XC) functionals assessed, five functionals, including the meta-GGA hybrid M06-2X, double hybrid B2PLYPD, and range-separated functionals CAM-B3LYP, ωB97XD, and LC-ωPBE, were found to be in excellent agreement with the EOM-CCSD gas-phase calculations. These functionals furnished excitation energies consistent with the pH dependence of the experimental spectra with a standard deviation (STDEV) of ∼0.20 eV. A molecular orbital analysis revealed a πσ* feature of the low-lying transitions of the BAs. The CAM-B3LYP functional showed the best overall performance and therefore shows promise for TDDFT calculations of processes involving photoexcitations of benzoic acid derivatives.

Mn(III) is a strong oxidant for one electron transfer, which may be important in the transformation of organic contaminants during water/wastewater treatment and biogeochemical redox processes. This study explored the reaction mechanisms of dissolved Mn(III) with organics. The role of dissolved Mn(III) either as a catalyst or an oxidant in reactions with organics was recognized. Aquo and/or hydroxo (or free) Mn(III), generated from the bisulfite activated permanganate process, facilitated efficient N-dealkylation of atrazine via a β-elimination mechanism, resulting no net redox reaction. In contrast, free Mn(III) degraded 4-chlorophenol via intramolecular redox processes, the same as hydroxyl radical (OH), resulting in dechlorination,OH substitution, ring-opening and mineralization. Mn(III)-pyrophosphate compounds did not react with atrazine because complexation by pyrophosphate rendered Mn(III) unable to bond with atrazine, thus the electron and proton transfers between the reactants couldn't occur. However, it degraded 4-chlorophenol at a slower rate compared to free Mn(III), due to its reduced oxidation potential. These results showed two distinct mechanisms on the degradation of organic contaminants and the insights may be applied in natural manganese-rich environments and water treatment processes with manganese compounds.

Rapid temperature rise in Arctic permafrost impacts not only the degradation of stored soil organic carbon (SOC) and climate feedback, but also the production and bioaccumulation of methylmercury (MeHg) toxin that can endanger humans, as well as wildlife in terrestrial and aquatic ecosystems. Currently little is known concerning the effects of rapid permafrost thaw on microbial methylation and how SOC degradation is coupled to MeHg biosynthesis. Here we describe the effects of warming on MeHg production in an Arctic soil during an 8-month anoxic incubation experiment. Net MeHg production increased >10 fold in both organic- and mineral-rich soil layers at warmer (8 °C) than colder (-2 °C) temperatures. The type and availability of labile SOC, such as reducing sugars and ethanol, were particularly important in fueling the rapid initial biosynthesis of MeHg. Freshly amended mercury was more readily methylated than preexisting mercury in the soil. Additionally, positive correlations between mercury methylation and methane and ferrous ion production indicate linkages between SOC degradation and MeHg production. These results show that climate warming and permafrost thaw could potentially enhance MeHg production by an order of magnitude, impacting Arctic terrestrial and aquatic ecosystems by increased exposure to mercury through bioaccumulation and biomagnification in the food web.

A new type of light diffracting hydrogel composite film consisting of nanoparticles and polymer has been fabricated through a combined physical–chemical polymerization process. In this fabrication approach, polymers with ionic functional groups for molecular recognition were successfully incorporated into a hydrogel of colloidal photonic crystals. We first embedded crystalline colloidal arrays into a nonionic polymer hydrogel by a physical freeze–thaw process using a formulation that contained poly(vinyl alcohol), dimethyl sulfoxide, water, and monodispersed polystyrene nanoparticles. Then, a second ionic polymer network, which interpenetrates into the first polymer network, was formed through a photochemical polymerization process. During the formation of the second polymer network, functional groups for molecular recognition were introduced. Finally, the physically cross-linked nonionic polymer network was removed by hydrothermal dissolution, leaving the chemically cross-linked ionic polymer network int...

The surfaces of Zn-doped biomagnetite nanostructured particles were functionalized with (3-mercaptopropyl)trimethoxysilane (MPTMS) and used as a high-capacity and collectable adsorbent for the removal of Hg(II) from water. Fourier transform infrared spectroscopy (FTIR) confirmed the attachment of MPTMS on the particle surface. The crystallite size of the Zn-doped biomagnetite was ∼17 nm, and the thickness of the MPTMS coating was ∼5 nm. Scanning transmission electron microscopy and dynamic light scattering analyses revealed that the particles formed aggregates in aqueous solution with an average hydrodynamic size of 826 ± 32 nm. Elemental analyses indicate that the chemical composition of the biomagnetite is Zn(0.46)Fe(2.54)O(4), and the loading of sulfur is 3.6 mmol/g. The MPTMS-modified biomagnetite has a calculated saturation magnetization of 37.9 emu/g and can be separated from water within a minute using a magnet. Sorption of Hg(II) to the nanostructured particles was much faster than other commercial sorbents, and the Hg(II) sorption isotherm in an industrial wastewater follows the Langmuir model with a maximum capacity of ∼416 mg/g, indicating two -SH groups bonded to one Hg. This new Hg(II) sorbent was stable in a range of solutions, from contaminated water to 0.5 M acid solutions, with low leaching of Fe, Zn, Si, and S (

This article is a mini-review mostly based on the work of the authors’ laboratory on the redox chemistry of metallodendrimers and gold nanoparticles, with emphasis on “click” chemistry. Late transition-metal sandwich complexes possess a rather unique ability to withstand two or three oxidation states without breakdown, especially with permethylated π-cyclopentadienyl or arene ligands. When they are linked to dendritic cores, the assembled nano-systems undergo chemically and electrochemically reversible transfer of a large number of electrons (up to 14,000). These multiple redox processes are useful for nanodevices behaving as nanobatteries for redox sensing, modified electrode surfaces and redox catalysis. Click chemistry was recently disclosed as one of the most powerful means to form such assemblies including both arene-cored and gold nanoparticle-cored dendrimers.

International audience; Mono‐, bis‐, and tris(4‐ferrocenyl‐1,2,3‐triazolylmethyl)arene–β‐cyclodextrin adducts have been used to prepare new Pd0 nanoparticle (PdNP) catalysts for C–C cross‐coupling reactions in EtOH/H2O. The results show that these catalysts work well in Miyaura–Suzuki and Heck reactions with iodoarenes at 25 and 80 °C, respectively, with turnover numbers (TONs) of up to 31000 for standard Miyaura–Suzuki reactions of PhI when 10 ppm of the Pd catalyst (5 nm PdNPs) were used. The results show the benefit for PdNP catalysis of encapsulating hydrophobic catalytic systems between peripheral water‐solubilizing cyclodextrins as bolamphiphile‐like materials because the open monoferrocenyltriazolylmethylbenzene system shows a considerably reduced catalytic efficiency compared with bis‐ and tris(4‐ferrocenyl‐1,2,3‐triazolylmethyl)arene–β‐cyclodextrin adducts.

International audience; Climate change is warming tundra ecosystems in the Arctic, resulting in the decomposition of previously-frozen soil organic matter (SOM) and release of carbon (C) to the atmosphere; however, the processes that control SOM decomposition and C emissions remain highly uncertain. In this study, we evaluate geochemical factors that influence microbial production of carbon dioxide (CO2) and methane (CH4) in the seasonally-thawed active layer of interstitial polygonal tundra near Barrow, Alaska. We report spatial and seasonal patterns of dissolved gases in relation to the geochemical properties of Fe and organic C in soil and soil solution, as determined using spectroscopic and chromatographic techniques. The chemical composition of soil water collected during the annual thaw season varied significantly with depth. Soil water in the middle of the active layer contained abundant Fe(III), and aromatic-C and low-molecular-weight organic acids derived from SOM decomposition. At these depths, CH4 was positively correlated with the ratio of Fe(III) to total Fe in waterlogged transitional and low-centered polygons but negatively correlated in the drier flat- and high-centered polygons. These observations contradict the expectation that CH4 would be uniformly low where Fe(III) was high due to inhibition of methanogenesis by Fe(III)-reduction reactions. Our results suggest that vertically-stratified Fe redox reactions influence respiration/fermentation of SOM and production of substrates (e.g., low-molecular-weight organic acids) for methanogenesis, but that these effects vary with soil moisture. We infer that geochemical differences induced by water saturation dictate microbial products of SOM decomposition, and Fe geochemistry is an important factor regulating methanogenesis in anoxic tundra soils.

Natural organic matter (NOM)-mediated redox cycling of elemental mercury Hg(0) and mercuric Hg(II) is critically important in affecting inorganic mercury transformation and bioavailability. However, these processes are not well understood, particularly in anoxic water and sediments where NOM can be reduced and toxic methylmercury is formed. We show that under dark anoxic conditions reduced organic matter (NOM(re)) simultaneously reduces and oxidizes Hg via different reaction mechanisms. Reduction of Hg(II) is primarily caused by reduced quinones. However, Hg(0) oxidation is controlled by thiol functional groups via oxidative complexation, which is demonstrated by the oxidation of Hg(0) by low-molecular-weight thiol compounds, glutathione, and mercaptoacetic acid, under reducing conditions. Depending on the NOM source, oxidation state, and NOM:Hg ratio, NOM reduces Hg(II) at initial rates ranging from 0.4 to 5.5 h(-1), which are about 2 to 6 times higher than those observed for photochemical reduction of Hg(II) in open surface waters. However, rapid reduction of Hg(II) by NOM(re) can be offset by oxidation of Hg(0) with an estimated initial rate as high as 5.4 h(-1). This dual role of NOM(re) is expected to strongly influence the availability of reactive Hg and thus to have important implications for microbial uptake and methylation in anoxic environments.

A short overview of the copper(I)-catalyzed azide alkyne cycloaddition (CuAAC), the most used “click” reaction, is presented, including the introduction of the “click” concept, the conditions of copper(I) catalysis, the regioselectivity, the nature of the catalysts and ligands, mechanistic features, experimental conditions and applications to organic synthesis and organic materials.

The ferrocenyl-triazolyl dendrimers synthesized by Huisgen-type Cu I -catalyzed 1,3-dipolar cycloaddition of ferrocenyl acetylenes with azido-terminated dendritic cores serve as redox exo-receptors for the recognition of both transition-metal cations and oxo-anions. This mini-review focuses on this work originated from the authors’ laboratory.

o-Carborane was covalently linked to the side chain of a polystyrene polymer by the “click” reaction to provide acarborane-appended polystyrene polymer. The initial step involved the radical polymerization of p-chloromethylstyrene with AIBN followed by replacement of the chloro units by azido groups; the final step employed the CuI-catalyzedHuisgen-type “click” reaction between the azidomethyl-appended polystyrene polymer and the ethynyl-terminated carborane unit yielding the desired carborane-appended polystyrene. Size exclusion chromatography (SEC) of this carborane-appended polymer showed a polydispersity index (PDI) of 1.52. Dynamic light scattering (DLS) in dichloromethane provided a diameter value of 4.5 nm. The MALDI TOF mass spectrum exhibited a series of single peaks culminating from 16 carborane-appended styrenyl units. The thermogravimetric analysis (TGA) showed the polymer to have good thermal robustness. Polymer-stabilized gold and palladium nanoparticles (AuNPs and PdNPs) were synthesized with sizes determined by TEM to be 2.6 ± 0.4 and 1.7 ± 0.3 nm, respectively. The Miyaura–Suzuki cross-coupling of phenyl iodide with phenylboronoic acid at 22 °C was catalyzed by the polymer-stabilized PdNPs.

The formation of methylmercury (MeHg), which is biomagnified in aquatic food chains and poses a risk to human health, is effected by some iron- and sulfate-reducing bacteria (FeRB and SRB) in anaerobic environments. However, very little is known regarding the mechanism of uptake of inorganic Hg by these organisms, in part because of the inherent difficulty in measuring the intracellular Hg concentration. By using the FeRB Geobacter sulfurreducens and the SRB Desulfovibrio desulfuricans ND132 as model organisms, we demonstrate that Hg(II) uptake occurs by active transport. We also establish that Hg(II) uptake by G. sulfurreducens is highly dependent on the characteristics of the thiols that bind Hg(II) in the external medium, with some thiols promoting uptake and methylation and others inhibiting both. The Hg(II) uptake system of D. desulfuricans has a higher affinity than that of G. sulfurreducens and promotes Hg methylation in the presence of stronger complexing thiols. We observed a tight coupling between Hg methylation and MeHg export from the cell, suggesting that these two processes may serve to avoid the build up and toxicity of cellular Hg. Our results bring up the question of whether cellular Hg uptake is specific for Hg(II) or accidental, occurring via some essential metal importer. Our data also point at Hg(II) complexation by thiols as an important factor controlling Hg methylation in anaerobic environments.

International audience; A new water-soluble glycodendrimer containing 9 terminal modified xylose branches was prepared from nona-azide terminated dendrimer by ‘click’ chemistry. The glycodendrimer was analyzed by 1H, 13C NMR and mass spectroscopy and used to stabilize palladium (PdNPs) and platine (PtNPs) nanoparticles. These DSN are stable in water and were characterized by TEM. The platinum NPs showed a remarkable catalytically activity for olefin hydrogenation in water at room temperature.

The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i) The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP) or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM), cross metathesis (CM), enyne metathesis reactions (EYM) – for reactions in water without a co-solvent and (ii) construction and functionalization of dendrimers by CM reactions.

The Gaussian-weighted operator derived by Rassolov and Chipman (RC operator) is applied to the spin density of large organic π-radicals using B3LYP and PBE0 density functionals and compared to the performance of the delta-function operator. The influence of the basis sets is examined. It is shown that both the delta-function operator and the RC operator provide comparable spin densities with the basis sets ext-6-31 1++G** and ext-6-31 1++G(2d,2p). An optimum range parameter of 0.25 or 0.35 a 0 is appropriate for the RC operator with the extended basis sets. For standard basis sets 6-311++G** and 6-311++G(2d,2p), the delta-function operator may yield considerable errors for heavy atoms due to the deficiency of the basis sets near the nuclei. To a large extent, however, this deficiency can be cured with the RC operator. With the same range parameter of 0.25 or 0.35 a 0 previously recommended, the errors are significantly reduced with respect to the delta-function method. If a relatively larger range parameter of 0.45 a 0 is used, a further improvement can be obtained and the spin densities at the B3LYP/6-311++G** or B3LYP/6-311++G(2d,2p) level of methods are similar to the ones at the B3LYP/ext-6-311++G** or B3LYP/ext-6-311++G(2d,2p) level of methods. Generally, the UB3LYP/6-311++G** and the UB3LYP/ext-6-311++G** methods are able to provide satisfactory spin densities. For some anions, the B3LYP/6-311++G(2d,2p) and the B3LYP/ext-6-311++G(2d,2p) methods are needed to achieve better agreement with the experiment. It is demonstrated that the B3LYP functional combined with the standard Pople-type basis sets 6-311++G** and 6-311++G(2d,2p), which are designed for conventional electronic structure calculations, serves as an efficient and reliable method for the calculation of spin densities of large organic radicals when the Rassolov—Chipman operator is utilized, while the delta-function operator may lead to far less reliable results. An optimum range parameter of 0.45 a 0 is recommended.

Archaeal communities from mercury and uranium-contaminated freshwater stream sediments were characterized and compared to archaeal communities present in an uncontaminated stream located in the vicinity of Oak Ridge, TN, USA. The distribution of the Archaea was determined by pyrosequencing analysis of the V4 region of 16S rRNA amplified from 12 streambed surface sediments. Crenarchaeota comprised 76% of the 1,670 archaeal sequences and the remaining 24% were from Euryarchaeota. Phylogenetic analysis further classified the Crenarchaeota as a Freshwater Group, Miscellaneous Crenarchaeota group, Group I3, Rice Cluster VI and IV, Marine Group I and Marine Benthic Group B; and the Euryarchaeota into Methanomicrobiales, Methanosarcinales, Methanobacteriales, Rice Cluster III, Marine Benthic Group D, Deep Sea Hydrothermal Vent Euryarchaeota 1 and Eury 5. All groups were previously described. Both hydrogen- and acetate-dependent methanogens were found in all samples. Most of the groups (with 60% of the sequences) described in this study were not similar to any cultivated isolates, making it difficult to discern their function in the freshwater microbial community. A significant decrease in the number of sequences, as well as in the diversity of archaeal communities was found in the contaminated sites. The Marine Group I, including the ammonia oxidizer Nitrosopumilus maritimus, was the dominant group in both mercury and uranium/nitrate-contaminated sites. The uranium-contaminated site also contained a high concentration of nitrate, thus Marine Group I may play a role in nitrogen cycle. Electronic supplementary material The online version of this article (doi:10.1007/s00248-010-9734-2) contains supplementary material, which is available to authorized users.

Alkyne protection by complexation of ethynylferrocene with dicobalt octacarbonyl followed by regioselective acetylation, then deprotection and “click” reaction with a nona-azido-terminated arene-cored dendrimer leads to the heterodifunctional nona(1,2,3-triazolyl-acetylferrocenyl) dendrimer. Cyclic voltammetry of this metallodendrimer shows recognition of both ATP2− and Pd2+. HAuCl4 is reduced much more slowly to gold nanoparticles by the nona(triazolyl-acetylferrocenyl dendrimer than by the nona(triazolylferrocenyl) dendrimer due to the shift of redox potential in the new heterodifunctional dendrimer compared to that of the parent ferrocenyl dendrimer.

The bacterial metalloregulator MerR is the index case of an eponymous family of regulatory proteins, which controls the transcription of a set of genes (the mer operon) conferring mercury resistance in many bacteria. Homodimeric MerR represses transcription in the absence of mercury and activates transcription upon Hg(II) binding. Here, the average structures of the apo and Hg(II)-bound forms of MerR in aqueous solution are examined using small-angle X-ray scattering, indicating an extended conformation of the metal-bound protein and revealing the existence of a novel compact conformation in the absence of Hg(II). Molecular dynamics (MD) simulations are performed to characterize the conformational dynamics of the Hg(II)-bound form. In both small-angle X-ray scattering and MD, the average torsional angle between DNA-binding domains is approximately 65 degrees. Furthermore, in MD, interdomain motions on a timescale of approximately 10 ns involving large-amplitude (approximately 20 A) domain opening-and-closing, coupled to approximately 40 degrees variations of interdomain torsional angle, are revealed. This correlated domain motion may propagate allosteric changes from the metal-binding site to the DNA-binding site while maintaining DNA contacts required to initiate DNA underwinding.

Titrations of commercial diaminobutane (DAB) and polyamidoamine (PAMAM) dendrimers by vitamins C (ascorbic acid, AA), B(3) (nicotinic acid), and B(6) (pyridoxine) were monitored by (1)H NMR spectroscopy using the chemical shifts of both dendrimer and vitamin protons and analyzed by comparison with the titration of propylamine. Quaternarizations of the terminal primary amino groups and intradendritic tertiary amino groups, which are nearly quantitative with vitamin C, were characterized by more or less sharp variations (Deltadelta) of the (1)H chemical shift (delta) at the equivalence points. The peripheral primary amino groups of the DAB dendrimers were quaternarized first, but not selectively, whereas a sharp chemical-shift variation was recorded for the inner methylene protons near the tertiary amines, thereby indicating encapsulation, when all the dendritic amines were quaternarized. With DAB-G5-64-NH(2), some excess acid is required to protonate the inner amino groups, presumably because of basicity decrease due to excess charge repulsion. On the other hand, this selectivity was not observed with PAMAM dendrimers. The special case of the titration of the dendrimers by vitamin B(6) indicates only dominant supramolecular hydrogen-bonding interactions and no quaternarization, with core amino groups being privileged, which indicates the strong tendency to encapsulate vitamins. With vitamin B(3), a carboxylic acid, titration of DAB-G3-16-NH(2) shows that only six peripheral amino groups are protonated on average, even with excess vitamin B(3), because protonation is all the more difficult due to increased charge repulsion, as positive charges accumulate around the dendrimer. Inner amino groups interact with this vitamin, however, thus indicating encapsulation presumably with supramolecular hydrogen bonding without much charge transfer.

Due to the weak interaction between DNA molecules and the inner surface of nanopores, DNA translocation is very fast, just leaving a short current drop without sufficient information to recognise the nucleotide sequence in the strand. In this paper, we propose a nanopore-nanofiber mesh hybridized structure to decelerate DNA translocation speed. Experimental results reveal that due to hydrophobic interaction between the DNA fragments and the nanofibers, the DNA moving speed can be retarded to two orders of magnitude slower. Furthermore, according to theory simulations, the additional fiber layer will reduce the electric field in the channel but elongate the capture region at the pore orifice, which will be helpful for increasing the capture rate and extending the DNA dwelling time in the meanwhile.

Well-defined asymmetric amphiphilic ABA′ block copolymers composed of poly(ethylene oxide) monomethylene ether (MPEO) with different molecular weights as A or A′ block and poly(styrene) (PS) as B block were synthesized by the combination of atom transfer radical polymerization (ATRP) and click reactions. First, bromine-terminated diblock copolymer poly(ethylene oxide) monomethylene ether-block-poly(styrene) (MPEO-PS-Br) was prepared by ATRP of styrene initiated with macroinitiator MPEO-Br, which was prepared from the esterification of MPEO and 2-bromoisobutyryl bromide. Then, the azido-terminated diblock copolymers MPEO-PS-N3 were prepared through the bromine substitution reaction with sodium azide. Propargyl-terminated MPEO with a different molecular weight was prepared under the basic condition from propargyl alcohol and p-toluenesulfonyl-terminated MPEO, which was prepared through the esterification of MPEO and p-toluenesulfochloride using pyridine as solvent. Asymmetric amphiphilic ABA′ block copolymers, with a wide range of number–average molecular weights from 1.92 × 104 to 2.47 × 104 and a narrow polydispersity from 1.03 to 1.05, were synthesized via a click reaction of the azido-terminated diblock copolymers and the propargyl-terminated MPEO in the presence of CuBr and 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA) catalyst system. The structures of these ABA′ block copolymers and corresponding precursors were characterized by NMR, IR, and GPC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Well-defined ABC block copolymers consisting of poly(ethylene oxide) monomethylene ether (MPEO) as A block, poly(styrene) (PS) as B block and poly(γ-benzyl- l -glutamate) (PBLG) as C block were synthesized by the combination of atom transfer radical polymerization (ATRP) and click reactions. The bromine-terminated diblock copolymer poly(ethylene oxide) monomethylene ether-block-poly(styrene) (MPEO–PS–Br) was prepared by ATRP of styrene initiated with macro-initiator MPEO–Br, which was prepared from the esterification of MPEO and 2-bromoisobutyryl bromide, and converted into the azido-terminated diblock copolymer MPEO–PS–N 3 by simple nucleophilic substitutions in DMF in the presence of sodium azide. Propargyl-terminated PBLGs were synthesized by ring-opening polymerization of γ-benzyl- l -glutamate- N -carboxyanhydride in DMF at room temperature using propargyl amine as an initiator. ABC triblock copolymers MPEO–PS–PBLG with a wide range of number-average molecular weights from 1.55 to 3.75 × 10 4 and a narrow polydispersity from 1.07 to 1.10 were synthesized via the click reaction of MPEO–PS–N 3 and the propargyl-terminated PBLG in the presence of CuBr and 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA) catalyst system. The structures of these ABC block copolymers and corresponding precursors were characterized by NMR, IR and GPC. The results showed that click reaction was efficient. Therefore, a facile approach was offered to synthesize ABC triblock copolymers composed of crystallizable polymer MPEO, conventional vinylic polymer PS and rod-like α-helix polypeptide PBLG.

A series of novel ABC 2 -type liquid-crystalline block copolymers with azobenzene moieties in the side chains were prepared by combination of atom transfer radical polymerization (ATRP) and the chemical modification reaction. First, the bromine-terminated diblock copolymer poly(ethylene oxide) monomethyl ether- block -polystyrene (MPEO-PS-Br) was prepared by ATRP of styrene initiated with macroinitiator MPEO-Br, which was obtained from the esterification of MPEO and 2-bromoisobutyryl bromide. Then, the bromo end groups of the resulting MPEO-PS-Br were derivatized into twice as many bromoisobutyrates by the chain end modification reaction to obtain ω,ω′-bis(bromo)-PS-MPEO (MPEO-PS-Br 2 ). The azobenzene-containing blocks of poly[6-(4-methoxy-azobenzene-4′-oxy) hexyl methacrylate] (PMMAZO) with different molecular weights were introduced into the derivative diblock copolymer by a second ATRP to synthesize the novel ABC 2 -type liquid-crystalline block copolymers poly(ethylene oxide) monomethyl ether- block -polystyrene- block -{poly[6-(4-methoxy-azobenzene-4′-oxy) hexyl methacrylate]} 2 [MPEO-PS-(PMMAZO) 2 ].

Prediction of colloid release and transport as affected by reactive species remains a significant challenge for field applications. In this paper, we report experimental and modeling results of ferrihydrite colloid release under the influence of citrate species. Using a 3-plane surface complexation model, equilibrium constants were obtained for the three proposed inner-sphere complexes by fitting a citrate adsorption isotherm on ferrihydrite at pH 4, and a pH adsorption envelop with 0.64 mM citrate. The constants were used in a reactive transport model for simulating reaction fronts of dissolved species during injection of citrate in ferrihydrite-coated quartz columns. Simulation results show that sorption alone may not adequately describe the breakthrough curves. Inclusions of ferrihydrite dissolution and re-adsorption of Fe(III) improve the prediction of dissolved species transport. Additionally, matrix diffusion may be needed for improved prediction. For the release of colloidal iron oxides it was shown that both oxide dissolution and interfacial repulsion controlled the process during complete breakthrough. However, the peak release of colloids, which occurred during the actual breakthrough of dissolved species, was mainly brought about by electric double layer forces. These particles underwent detachment–deposition–detachment cycles along the flow path, and emerged in the effluent with the major reaction front. To quantitatively predict colloid release, a semi-empirical linear correlation was established, linking the calculated electric potential to experimental colloid release rates. The model may be applied to the prediction and scaling of aquifer remediation studies involved in the injection of organic ligands to mobilize particle bound contaminants.

Effects of the anionic surfactants, sodium dodecyl sulfate and sodium oleate, on the formation and properties of silica colloidal nanoparticles were investigated. At a concentration of approximately 1 x 10(-3) M, adsorption of anionic surfactants increased particle size, monodispersity, and negative surface charge density of synthesized silica particles. As uniformity of particle size and particle-particle interactions increase, colloidal photonic crystals readily self-assemble without extensive washing of the synthesized silica nanoparticles. The photonic crystals diffract light in the visible region according to Bragg's law. The assembled colloidal particle arrays exhibit a face-centered cubic structure in dried thin films. This study offers a new approach for producing ordered colloidal silica thin films.

A new strategy to synthesize a series of well-defined amphiphilic PEO-b-PS-b-PCL block copolymers is presented. First, bromine-terminated diblock copolymers PEO-b-PS-Br are prepared by ATRP of styrene, and converted into azido-terminated PEO-b-PS-N 3 diblock copolymers. Then propargyl-terminated PCL is prepared by ROP of e-caprolactone. The PEO-b-PS-b-PCL triblock copolymers with M n from 1.62 x 10 4 to 1.96 × 10 4 and a narrow PDI from 1.09 to 1.19 are finally synthesized from these precursors. The structures of these triblock copolymers and their precursors have been characterized by NMR, IR, and GPC analysis.

We propose and develop the complex-scaled multiconfigurational spin-tensor electron propagator (CMCSTEP) technique for theoretical determination of resonance parameters with electron-atom and electron-molecule systems including open-shell and highly correlated atoms and molecules. The multiconfigurational spin-tensor electron propagator (MCSTEP) method developed and implemented by Yeager and co-workers in real space gives very accurate and reliable ionization potentials and attachment energies. The CMCSTEP method uses a complex-scaled multiconfigurational self-consistent field (CMCSCF) state as an initial state along with a dilated Hamiltonian where all of the electronic coordinates are scaled by a complex factor. The CMCSCF was developed and applied successfully to resonance problems earlier. We apply the CMCSTEP method to get ${}^{2}P\phantom{\rule{0.16em}{0ex}}{\text{Be}}^{\ensuremath{-}}$ shape resonance parameters using $14s11p5d,\phantom{\rule{0.16em}{0ex}}14s14p2d$, and $14s14p5d$ basis sets with a $2s2p3d$ complete active space. The obtained values of the resonance parameters are compared to previous results. Here CMCSTEP has been developed and used for a resonance problem. It appears to be among the most accurate and reliable techniques. Vertical ionization potentials and attachment energies in real space are typically within $\ifmmode\pm\else\textpm\fi{}0.2\phantom{\rule{0.28em}{0ex}}\text{eV}$ or better of excellent experimental results and full configuration-interaction calculations with a good basis set. We expect the same sort of agreement in complex space.

Nanoscale zero-valent iron (NZVI) is effective in reductively degrading dense non-aqueous phase liquids (DNAPLs), such as trichloroethene (TCE), in groundwater (i.e., dechlorination) although the NZVI technology itself still suffers from high material costs and inability to target hydrophobic contaminants in source zones. To address these problems, we developed a novel, inexpensive iron-carbon (Fe-C) nanocomposite material by simultaneously milling micron-size iron and activated carbon powder. Microscopic and X-ray diffraction (XRD) characterization of the composite material revealed that nanoparticles of Fe were dispersed in activated carbon and a new iron carbide phase was formed. Bench-scale studies showed that this material instantaneously sorbed >90% of TCE from aqueous solutions and subsequently decomposed TCE into non-chlorinated products. Compared to milled Fe, Fe-C nanocomposite dechlorinated TCE at a slightly slower rate and favored the production of ethene over other TCE degradation products such as C3--C6 compounds. When placed in hexane-water mixture, the Fe-C nanocomposite materials are preferentially partitioned into the organic phase, indicating the ability of the composite materials to target DNAPL during remediation.

Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between –1 and 0 in a water-soluble fraction (WSF) demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF) did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions.

Mercury from anthropogenic activities is a pollutant that poses significant risks to humans and the environment. In soils, mercury remediation can be technically challenging and costly, depending on the subsurface mercury distribution, the types of mercury species, and the regulatory requirements. This paper introduces the chemistry of mercury and its implications for in situ mercury remediation, which is followed by a detailed discussion of several in situ Hg remediation technologies in terms of applicability, cost, advantages, and disadvantages. The effect of Hg speciation on remediation performance, as well as Hg transformation during different remediation processes, was detailed. Thermal desorption, electrokinetic, and soil flushing/washing treatments are removal technologies that mobilize and capture insoluble Hg species, while containment, solidification/stabilization, and vitrification immobilize Hg by converting it to less soluble forms. Two emerging technologies, phytoremediation and nanotechnology, are also discussed in this review.

Microbial carbonates are long-ranging, essentially bacterial, aquatic sediments. Their calcification is dependent on ambient water chemistry and their growth is influenced by competition with other organisms, such as metazoans. In this paper, these relationships are examined by comparing the geological record of microbial carbonates with metazoan history and secular variations in CaCO3 saturation state of seawater. Marine abundance data show that microbial carbonates episodically declined during the Phanerozoic Eon (past 545 Myr) from a peak 500 Myr ago. This abundance trend is generally inverse to that of marine metazoan taxonomic diversity, supporting the view that metazoan competition has progressively limited the formation of microbial carbonates. Lack of empirical values concerning variables such as seawater ionic composition, atmospheric partial pressure of CO2, and pH currently restricts calculation of CaCO3 saturation state for the Phanerozoic as a whole to the use of modeled values. These data, together with palaeotemperature data from oxygen isotope analyses, allow calculation of seawater CaCO3 saturation trends. Microbial carbonate abundance shows broad positive correspondence with calculated seawater saturation state for CaCO3 minerals during the interval 150–545 Myr ago, consistent with the likelihood that seawater chemistry has influenced the calcification and therefore accretion and preservation of microbial carbonates. These comparisons suggest that both metazoan influence and seawater saturation state have combined to determine the broad pattern of marine microbial carbonate abundance throughout much of the Phanerozoic. In contrast, for the major part of the Precambrian it would seem reasonable to expect that seawater saturation state, together with microbial evolution, was the principal factor determining microbial carbonate development. Interrelationships such as these, with feedbacks influencing organisms, sediments, and the environment, are central to geobiology.

Carbon dioxide sequestration at intermediate ocean depths in the form of a sinking CO2 stream has been shown to be technically feasible. Buoyancy characteristics of CO2 hydrate particles obtained from a coflow reactor operating under conditions that produce negatively buoyant CO2 hydrate composite particles were studied. Using a simplified process model, the limiting ratios of CO2 to water to produce sinking hydrate composite streams were established for pressure and temperature conditions of intermediate ocean depths. A kinetic model involving a mass transfer step and a reaction step was proposed to explain experimental data using a seafloor process simulator. Results suggest that the reactor operates under mass‐transfer controlled conditions. Although the density of freshwater is only a few percentage units less than that of seawater, operating conditions derived from freshwater‐based studies are significantly different for ambient seawater. Owing to the higher density of seawater, greater conv...

This study investigated the effect of cationic, anionic (saturated and unsaturated), and nonionic surfactants on the formation, morphology, and surface properties of silica nanoparticles synthesized by the ammonium‐catalyzed hydrolysis of tetraethoxysilane in alcoholic media. Results indicate that at a relatively low surfactant concentration (1 × 10−3–1 × 10−6 M), cationic surfactants significantly affected the growth of silica particles as measured by dynamic light scattering and transmission electron microscopic analyses. In contrast, the anionic and nonionic surfactants showed relatively minor effects in the low concentration range. The magnitude of negative zeta potential was reduced for silica colloids that were synthesized in the presence of cationic surfactant because of charge neutralization. The presence of anionic surfactants only slightly increased the negative zeta potential while the nonionic surfactant showed no obvious effects. At high surfactant concentrations (>1 × 10−3 M), catio...

Although the sorption of cetyltrimethylammonium ion (CTA+) on silica (SiO2) surfaces has been studied extensively, little is known about the interactions between large surfactant molecules and nanosized colloidal particles with a high specific surface area. The aim of the study was to understand the effects of structural arrangements of sorbed CTA+ ions on the stability and surface properties of SiO2 nanoparticles. The extent of the effect of CTA+ sorption on the aggregation behavior of the SiO2 nanoparticle suspension was investigated with the dynamic light scattering (DLS) technique. Both the Fourier transform infrared (FTIR) and Raman spectroscopic techniques were used to probe the sorbed layers of CTA+ on silica surfaces. Results indicate that, at a low surface coverage (less than a monolayer), CTA+ molecules were strongly bound to the SiO2 surface via their trimethylammonium headgroups. A bilayer sorption of CTA+ was observed at a high surface coverage, and the sorption is attributed to the hydrophob...