Vibrational Structure of the B—X System of Isotopic Ago Molecules

Spectra of ¹⁰⁷Ag¹⁸O and ¹⁰⁷Ag¹⁶O molecules have been obtained in a low-pressure arc in oxygen atmosphere, and recorded with medium dispersion. Vibrational assignments for the bands of B ²π —X²π system were verified by the study of the oxygen isotope effect, and the vibrational constants were obtained for the states involved in transitions.     

Synthesis,Structure and Catalytic Activity of NHC–AgI Carboxylate Complexes

A general synthetic route was used to prepare 15 new N‐heterocyclic carbene (NHC)–Ag^I complexes bearing anionic carboxylate ligands [Ag(NHC)(O₂CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand‐accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–Ag^I complexes.     

Nanocomposites based on crosslinked polyacrylic latex/silver nanoparticles for waterborne high‐performance antibacterial coatings

Functional polymer/AgNPs nanocomposites have been prepared. Silver nanoparticles (NPs) were synthesized to which polyacrylamide, PAAm, was covalently bound. PAAm was synthesized via a RAFT reaction and carried thiol and carboxylic acid end groups. Thiol was used to bind the polymer to the metal surface and carboxyl for further reactions. The AgNPs were used in a post‐crosslinking reaction with a separately synthesized poly(butyl acrylate‐co‐methyl methacrylate)/polyglycidyl methacrylate core/shell latex bearing epoxy functional groups. Dynamic mechanical analysis showed that the functional AgNPs effectively crosslinked the latex polymer, and that the final product had excellent mechanical strength. Antibacterial tests revealed that the nanocomposite films had strong antibacterial activity against all types of the bacteria and the immobilization of silver NPs by crosslinking retarded the release of silver in comparison to the uncrosslinked ones. With the presented method, it is possible to obtain ductile antibacterial nanocomposites to be used as waterborne functional coatings. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1435–1447     

Minireview: Advances in Germanium Isotope Analysis by Multiple Collector–Inductively Coupled Plasma–Mass Spectrometry

The advent of multiple collector–inductively coupled plasma–mass spectrometry (MC-ICP-MS) has made the high-precision determination of Ge isotopes possible, which leads to the widespread application of Ge isotopes in earth, ocean, and cosmochemistry fields. This paper reviews the history of Ge isotope analysis, chemical dissolution and purification, and mass spectrometry measurements. Concentrated HNO₃ is sufficient to dissolve nearly all types of samples and HF is also involved for Si-rich samples. Low-temperature ashing prior to dissolution is an alternative way to preconcentrate Ge in organic-rich samples. For different matrices, Ge isotopes can be determined by MC-ICP-MS coupled with a traditional nebulizer system or hydride generation system after two-step separation, one step cation/anion-exchange separation, or Mg/Fe co-precipitation protocols. Ion-exchange column methods are suitable for samples with elevated matrix and Ge content such as sulfides, iron oxides, silicate rocks, and coals, whereas Mg or Fe coprecipitation methods are particularly suitable for all kinds of water. Hydride generation systems are improved over traditional nebulizer system due to the smaller sample quantity and fewer matrix-related interferences. Sample-standard bracketing, double spike, and external Ga isotope normalization are used to mass bias correction and yield consistent results. Analytical methods involving Ge-poor samples and Ge isotope analyses based on different Ge species or specific Ge compound in natural environment will be important prospects in the further study. For further applications of Ge isotopes in mineral deposits such as sulfide and iron oxide deposits, sulfides, and iron oxides reference materials should be developed in the future.     

Silver nanoparticles immobilized onto poly(4‐vinylpyridine)‐functionalized magnetic nanoparticles: A robust magnetically recyclable catalyst for oxidant‐free alcohol dehydrogenation

A heterogeneous and recyclable catalyst with a high loading of silver nanoparticles was synthesized via the silver nanoparticles being supported onto the surface of magnetic nanoparticles coated with poly(4‐vinylpyridine). The synthesized catalyst was used in the dehydrogenation of alcohols to corresponding carbonyl compounds. A broad diversity of alcohols was converted into their corresponding carbonyl compounds in excellent yields. The catalyst was easily recovered by applying an external magnetic field and reused for seven reaction cycles without considerable loss of activity. The catalyst was fully characterized using various techniques.     

Highly efficient and green oxidation of alkanes and alkylaromatics with hydrogen peroxide catalysed by silver and vanadyl on mesoporous silica‐coated magnetite

A heterogeneous catalyst (FeSi/Ag/VO) based on silver and vanadyl as active sites and mesoporous silica‐coated nanospheres of magnetite (Fe₃O₄@m‐SiO₂) as support was successfully prepared by deposition of Ag nanoparticles and the covalent grafting of vanadyl(IV) acetylacetonate on Fe₃O₄@m‐SiO₂. The catalyst exhibited excellent activity for the oxidation of alkanes, benzene and alkylaromatics using green oxidant H₂O₂ and oxalic acid in acetonitrile at 60 °C.     

Probing nanocolumnar silver nanoparticle/zinc oxide hierarchical assemblies with advanced surface plasmon resonance and their enhanced photocatalytic performance for formaldehyde removal

Recent advances in photocatalysis focus on the development of materials with hierarchical structure and on the surface plasmon resonance (SPR) phenomenon exhibited by metal nanoparticles (NPs). In this work, both are combined in a material where size‐controllable Ag‐NPs are uniformly loaded onto the hierarchical microporous and mesoporous and nanocolumnar structures of ZnO, resulting in Ag‐NP/ZnO nanocomposites. The embedded Ag‐NPs slightly decrease the hydrophobicity of fibrous ZnO, improve its wettability, and increase the absorption of formaldehyde (H₂CO) onto the photocatalyst, all of this resulting in excellent photodegradation of formaldehyde in aqueous solution. Besides, we found that Ag‐NPs with optimal size not only accelerate the charge transfer to the surface of ZnO, but also strengthen the SPR effect in the intercolumnar channels of fibrous ZnO particles combining with high concentration of photo‐generated radical species. The micro‐to‐mesoporous ZnO is like a nanoarray packed Ag‐NPs. With Ag‐NPs of diameter 2.5 < ? < 6.5 nm, ZnO exhibits the most superior photodegradation rate constant value of 0.0239 min^?1 with total formaldehyde removal of 97%. This work presents a new feasible approach involving highly sophisticated Ag‐NP/ZnO architecture combining the SPR effect and hierarchically ordered structures, which results in high photocatalytic activity for formaldehyde photodegradation.     

Through-Space Spin Coupling in a Silver(II) Porphyrin Dimer upon Stepwise Oxidations: AgII⋅⋅⋅AgII,AgII⋅⋅⋅AgIII,and AgIII⋅⋅⋅AgIII Metallophilic Interactions

Metallophilic interactions between closed-shell metal ions are becoming a popular tool for a variety of applications related to high-end materials. Heavier d⁸ transition-metal ions are also considered to have a closed shell and can be involved in such interactions. There is no systematic investigation so far to estimate the structure and energy characteristics of metallophilic interactions in Ag^II/Ag^II (d⁹/d⁹), Ag^III/Ag^III (d⁸/d⁸), and mixed-valent Ag^II/Ag^III (d⁹/d⁸) complexes, which have been demonstrated in the present study. Both interporphyrinic and intermetallic interactions were investigated on stepwise oxidation by using a rigid ethene-bridged cis silver(II) porphyrin dimer and the results compared with those for highly flexible ethane-bridged analogues. By controlling the nature of chemical oxidants and their stoichiometry, both 1e and 2e oxidations were done stepwise to generate Ag^II/Ag^III mixed-valent and Ag^III/Ag^III porphyrin dimers, respectively. Unlike all other ethene-bridged metalloporphyrin dimers reported earlier, in which 2e oxidation stabilizes only the trans form, such an oxidation of silver(II) porphyrin dimer stabilizes only the cis form because of the metallophilic interaction. Besides silver(II) ⋅⋅⋅ silver(II) interactions in cis silver(II) porphyrin dimer, stepwise oxidations also enabled us to achieve various hitherto-unknown silver(II) ⋅⋅⋅ silver(III) and silver(III) ⋅⋅⋅ silver(III) interactions, which thereby allow significant modulation of their structure and properties. The strength of Ag ⋅⋅⋅ Ag interaction follows the order Ag^II/Ag^II (d⁹/d⁹)<Ag^II/Ag^III (d⁹/d⁸)<Ag^III/Ag^III (d⁸/d⁸). Single-crystal XRD, X-ray photoelectron spectroscopy (XPS), ¹H NMR and EPR spectroscopy, and variable-temperature magnetic investigations revealed various oxidation states of silver and metallophilic interactions, which are also well supported by computational analysis.     

Bio-Organometallic Derivatives of Antibacterial Drugs

Overuse and misuse of antibacterial drugs has resulted in bacteria resistance and in an increase in mortality rates due to bacterial infections. Therefore, there is an imperative necessity of new antibacterial drugs. Bio-organometallic derivatives of antibacterial agents offer an opportunity to discover new active antibacterial drugs. These compounds are well-characterized products and, in several examples, their antibacterial activities have been studied. Both inhibition of the antibacterial activity and strong increase in the antibiotic activity of the parent drug have been found. The synthesis of the main classes of bio-organometallic derivatives of these drugs, as well as examples of the use of structure–activity relation (SAR) studies to increase the activity and to understand the mode of action of bio-organometallic antimicrobial peptides (BOAMPs) and platensimicyn bio-organometallic mimics is presented in this article.     

Self‐Assembled Silver–Gold Nanoisland Films on Glass for SERS Applications

We present a study of resonant optical properties of gold‐protected silver nanoisland films. Silver nanoislands were grown on a glass substrate using out‐diffusion technique, the growth was followed by the deposition of nanometer‐thick gold coatings. Scanning electron microscopy and optical spectroscopy were used to characterize morphology and extinction spectra of the grown combined silver–gold nanostructures. Micro Raman spectroscopy of the combined nanoislands has demonstrated their signal enhancement factor exceeding that one of the initial silver nanoislands.