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This new book on this hot topic summarizes the key achievements for the synthesis and catalytic applications of pincer and pincer-type complexes, providing readers with the latest research highlights.

With controlled nanometre-sized pores and surface areas of thousands of square metres per gram, metal-organic frameworks (MOFs) may have an integral role in future catalysis, filtration and sensing applications. In general, for MOF-based device fabrication, well-organized or patterned MOF growth is required, and thus conventional synthetic routes are not suitable. Moreover, to expand their applicability, the introduction of additional functionality into MOFs is desirable. Here, we explore the use of nanostructured poly-hydrate zinc phosphate (α-hopeite) microparticles as nucleation seeds for MOFs that simultaneously address all these issues. Affording spatial control of nucleation and significantly accelerating MOF growth, these α-hopeite microparticles are found to act as nucleation agents both in solution and on solid surfaces. In addition, the introduction of functional nanoparticles (metallic, semiconducting, polymeric) into these nucleating seeds translates directly to the fabrication of functional MOFs suitable for molecular size-selective applications. Metal-organic frameworks (MOFs) have potential catalysis, filtration and sensing applications, but device fabrication will require controlled MOF growth. Here, α-hopeite microparticles are used to achieve spatial control of MOF nucleation, and accelerate MOF growth.

Well-preserved fossils of pivotal early bird and nonavian theropod species have provided unequivocal evidence for feathers and/or downlike integuments. Recent studies have reconstructed color on the basis of melanosome structure; however, the chemistry of these proposed melanosomes has remained unknown. We applied synchrotron x-ray techniques to several fossil and extant organisms, including Confuciusornis sanctus, in order to map and characterize possible chemical residues of melanin pigments. Results show that trace metals, such as copper, are present in fossils as organometallic compounds most likely derived from original eumelanin. The distribution of these compounds provides a long-lived biomarker of melanin presence and density within a range of fossilized organisms. Metal zoning patterns may be preserved long after melanosome structures have been destroyed.

Uranyl acetate is the standard contrasting agent in electron microscopy (EM), but it is toxic and radioactive. We reasoned neodymium acetate might substitute uranyl acetate as a contrasting agent, and we find that neodymium acetate indeed can replace uranyl acetate in several routine applications. Since neodymium acetate is not toxic, not radioactive and easy to use, we foresee neodymium will replace uranyl in many EM sample preparation applications worldwide.

Dissolved organic matter (DOM) is ubiquitous in natural waters and plays a central role in the biogeochemistry in riverine, estuarine and marine environments. This study quantifies and characterizes solid-phase extractable DOM and trace element complexation at different salinities in the Weser and Elbe River, northern Germany, and the North Sea. Dissolved organic carbon (DOC), total dissolved nitrogen (TDN), Co and Cu concentrations were analyzed in original water samples. Solid-phase extracted (SPE) water samples were analyzed for DOC (DOCSPE), dissolved organic nitrogen (DONSPE), sulfur (DOSSPE) and trace metal (51V, 52Cr, 59Co, 60Ni, 63Cu, 75As) concentrations. Additionally, different pre-treatment conditions (acidification vs. non-acidification prior to SPE) were tested. In agreement with previous studies, acidification led to generally higher recoveries for DOM and trace metals. Overall, higher DOM and trace metal concentrations and subsequently higher complexation of trace metals with carbon and sulfur-containing organic complexes were found in riverine compared to marine samples. With increasing salinity, the concentrations of DOM decreased due to estuarine mixing. However, the slightly lower relative decrease of both, DOCSPE and DONSPE (~77%) compared to DOSSPE (~86%) suggests slightly faster removal processes for DOSSPE. A similar distribution of trace metal and carbon and sulfur containing DOM concentrations with salinity indicates complexation of trace metals with organic ligands. This is further supported by an increase in Co and Cu concentration after oxidation of organic complexes by UV treatment. Additionally, the complexation of metals with organic ligands (analyzed by comparing metal/DOCSPE and metal/DOSSPE ratios) decreased in the order Cu > As > Ni > Cr > Co and thus followed the Irving-Williams order. Differences in riverine and marine trace metal containing DOMSPE are summarized by their average molar ratios of (C107N4P0.013S1)1000V0.05Cr0.33Co0.19Ni0.39Cu3.41As0.47 in the riverine endmember and (C163N7P0.055S1)1000V0.05Cr0.47Co0.16Ni0.07Cu4.05As0.58 in the marine endmember.

Mineral-associated organic matter is associated with a suite of soil minerals that can confer stability, resulting in the potential for long-term storage of carbon (C). Not all interactions impart the same level of protection, however; evidence is suggesting that C in certain mineral pools is dynamic and vulnerable to disturbance in the decades following harvesting. The objective of this research was to describe and characterize organic matter-mineral interactions through depth in horizons of soils of contrasting stand age. Sequential selective dissolutions representing increasingly stable mineral-associated organic matter pools from water soluble minerals (deionized water), organo-metal complexes (Na-pyrophosphate), poorly-crystalline minerals (HCl hydroxylamine), and crystalline secondary minerals (Na-dithionite HCl)) were carried out for Ae, Bf and BC horizons sampled from a Young and Mature forest site (35 and 110 years post-harvest) in Mooseland, Nova Scotia, Canada. Sequential selective dissolution extracts were analyzed for C, δ13C, iron (Fe) and aluminum (Al). Organo-metal complexes (OMC) were the largest mineral-associated OM pool in all horizons. This pool dominated the C distribution in B horizons (~60-70% of Bf bulk C), with a minor contribution from poorly-crystalline (PCrys), crystalline (Crys) minerals and water soluble (WS) associations. C in OMC and PCrys pools explained the variation in bulk C in horizons through depth at both sites. Twice as much C in OMC pools was measured at the Mature site compared to the Young site in the Bf horizons, supported by higher C:(Fe+Al) ratios. Isotopic analysis indicated that this extraction procedure isolated distinct mineral-associated OM pools. δ13C signatures of pyrophosphate-extracted OMC pools ranged from -27‰ to -28‰, similar to δ13C of bulk C and to plant-derived humic acids and associated biomass. The water soluble phase (mean δ13C = -29 ‰) was up to 2 ‰ more depleted, whereas the δ13C of Crys pools were more enriched in 13C (-13‰ to -16 ‰) compared to bulk soil. The results from this study suggest that association with minerals does not necessarily confer stability: organo-metal pools dominate in podzol horizons through depth, and contribute most to C storage, but are potentially susceptible to destabilization following the physical changes resulting from forest harvesting disturbance.

Baby foods, from the Spanish market and prepared from meat, fish, vegetables, cereals, legumes, and fruits, were analyzed to obtain the concentration of antimony (Sb), arsenic (As), bismuth (Bi), and tellurium (Te) as toxic elements and selenium (Se) as essential element. An analytical procedure was employed based on atomic fluorescence spectroscopy which allowed to obtain accurate data at low levels of concentration. Values of 14 commercial samples, expressed in nanograms per gram fresh weight, ranged for Sb 0.66–6.9, As 4.5–242, Te 1.35–2.94, Bi 2.18–4.79, and Se 5.4–109. Additionally, speciation studies were performed based on data from a non-chromatographic screening method. It was concluded that tellurium and bismuth were mainly present as inorganic forms and selenium as organic form, and antimony and arsenic species depend on the ingredients of each baby food. Risk assessment considerations were made by comparing dietary intake of the aforementioned elements through the consumption of one baby food portion a day and recommended or tolerable guideline values.

Chemical reactions at ultrasmall volumes are becoming increasingly necessary to study biological processes, to synthesize homogenous nanostructures and to perform high-throughput assays and combinatorial screening. Here we show that a femtolitre reaction can be realized on a surface by handling and mixing femtolitre volumes of reagents using a microfluidic stylus. This method, named microfluidic pen lithography, allows mixing reagents in isolated femtolitre droplets that can be used as reactors to conduct independent reactions and crystallization processes. This strategy overcomes the high-throughput limitations of vesicles and micelles and obviates the usually costly step of fabricating microdevices and wells. We anticipate that this process enables performing distinct reactions (acid-base, enzymatic recognition and metal-organic framework synthesis), creating multiplexed nanoscale metal-organic framework arrays, and screening combinatorial reactions to evaluate the crystallization of novel peptide-based materials. Chemical reactions on femtolitre scales are necessary to study confined biological processes. Here, the authors use a microfluidic pen lithography technique to perform a series of discrete femtoscale acid-base and synthetic reactions, and crystallizations on a surface with high registration accuracy.

Our originally designed dansylamidoethylcyclen 4 as a biomimetic Zn2+-selective fluorophore has been demonstrated to be a good detector of the apoptosis (induced by an anticancer agent, etoposide, and H2O2) in cancer cells such as HeLa and HL60 cells. The macrocyclic Zn2+ ligand 4 (mostly as a deprotonated form) is cell-permeable to show weak fluorescence (emission at 550 nm), which forms a strong fluorescent 1:1 Zn2+ complex 5 (emission at 530 nm) when Zn2+ is incorporated into the cells by a zinc(II) ionophore pyrithione. Thus formed, Zn2+ complex 5 is cell-impermeable and remains intact over a few hours. When apoptosis in HeLa or HL60 cells is artificially induced, 4 selectively and strongly stains apoptotic cells only at early stages, which was verified by using the conventional apoptosis detection probe annexin V-Cy3. Detection of the apoptotic cells by 4 was perhaps due to significantly increased free Zn2+ flux at early stages of apoptosis. Apoptotic detection by 4 has been compared with a presently available Zn2+ fluorophore, Zinquin 1. We present that 4 has advantages in detection of apoptosis over annexin V-Cy3 and Zinquin 1.

To achieve a “Good Environmental Status by 2015,” as demanded by the water framework directive, monitoring programs are needed to furnish data on target compounds. In this study, a first evaluation of influents and main emissions of 3 local wastewater treatment plants (WWTP) in the Adour estuary (southwest of France) was performed for 23 pollutants (10 musk fragrances, 5 alkylphenols, and 8 organometallics), as well as receiving estuarine water from the same area. High frequency of occurrence of these compounds was found in influents samples (musks: 22–100%; alkylphenols 11–100%; organometallics 0–100%) and effluents (musks: 0–100%; alkylphenols 0–100%; organometallics 0–100%). The removal efficiencies were calculated and varied from negative values up to 98% with the lowest values for synthetic musk compounds. Temporal variability of the target compounds also was studied, and a few tendencies were observed. Estimation of the daily output of each WWTP into the estuary also showed that galaxolide, nonylphenol, monobuthyltin, and inorganic mercury were the compounds discharged into the environment at the highest concentrations. Finally, the occurrence of these compounds in estuarine waters was evaluated; most of them were present at concentrations below the limits of quantification (musks: 0.53–41.5 ng/L; alkylphenols 3.4–410 ng/L; organometallics 0.02–0.70 ng/L) suggesting a low impact in the resulting receiving waters.