Large Metal Ions Research Articles

Co-ordination behaviour of a novel tristhiourea tripodal ligand; structural variations in a series of transition metal complexes.

The co-ordination chemistry of a tristhiourea tris(2-pyridylmethyl)amine ligand () with a series of transition metal ions has been investigated. Crystallographic data show that large metal ions, with no geometrical preferences, such as Mn(ii) and Cd(ii), will form seven co-ordinate monocapped octahedral complexes, while smaller metal ions such as Zn(ii) favour five co-ordinate trigonal bipyramidal structures. In a similar manner to the related bisthiourea complexes, the Ni(ii) complex shows a strong preference for octahedral geometries resulting in the ligand binding asymmetrically. Spectroscopic (IR and NMR), spectrometric (MS) as well as electrochemical data for these complexes are reported.

Formation of todorokite from "c-disordered" H(+)-birnessites: the roles of average manganese oxidation state and interlayer cations.

BackgroundTodorokite, a 3 × 3 tectomanganate, is one of three main manganese oxide minerals in marine nodules and can be used as an active MnO6 octahedral molecular sieve. The formation of todorokite is closely associated with the poorly crystalline phyllomanganates in nature. However, the effect of the preparative parameters on the transformation of “c-disordered” H+-birnessites, analogue to natural phyllomanganates, into todorokite has not yet been explored.ResultsSynthesis of “c-disordered” H+-birnessites with different average manganese oxidation states (AOS) was performed by controlling the MnO4−/Mn2+ ratio in low-concentrated NaOH or KOH media. Further transformation to todorokite, using “c-disordered” H+-birnessites pre-exchanged with Na+ or K+ or not before exchange with Mg2+, was conducted under reflux conditions to investigate the effects of Mn AOS and interlayer cations. The results show that all of these “c-disordered” H+-birnessites exhibit hexagonal layer symmetry and can be transformed into todorokite to different extents. “c-disordered” H+-birnessite without pre-exchange treatment contains lower levels of Na/K and is preferably transformed into ramsdellite with a smaller 1 × 2 tunnel structure rather than todorokite. Na+ pre-exchange, i.e. to form Na-H-birnessite, greatly enhances transformation into todorokite, whereas K+ pre-exchange, i.e. to form K-H-birnessite, inhibits the transformation. This is because the interlayer K+ of birnessite cannot be completely exchanged with Mg2+, which restrains the formation of tunnel “walls” with 1 nm in length. When the Mn AOS values of Na-H-birnessite increase from 3.58 to 3.74, the rate and extent of the transformation sharply decrease, indicating that a key process is Mn(III) species migration from layer into interlayer to form the tunnel structure during todorokite formation.ConclusionsStructural Mn(III), together with the content and type of interlayer metal ions, plays a crucial role in the transformation of “c-disordered” H+-birnessites with hexagonal symmetry into todorokite. This provides further explanation for the common occurrence of todorokite in the hydrothermal ocean environment, where is usually enriched in large metal ions such as Mg, Ca, Ni, Co and etc. These results have significant implications for exploring the origin and formation process of todorokite in various geochemical settings and promoting the practical application of todorokite in many fields.Graphical abstractXRD patterns of Mg2+-exchanged and reflux treatment products for the synthetic “c-disordered” H+-birnessites.

Charge transfer complexes of fullerene[60] with porphyrins as molecular rectifiers. A theoretical study.

Molecular diodes based on charge transfer complexes of fullerene[60] with different metalloporphyrins have been modeled. Their current-voltage characteristics and the rectification ratios (RR) were calculated using direct ab initio method at PBE/def2-SVP level of theory with D3 dispersion correction, for voltages ranging from -2 to +2 V. The highest RR of 32.5 was determined for the complex of fullerene[60] with zinc tetraphenylporphyrin at 0.8 V. Other molecular diodes possessed lower RR, however, all complexes showed RR higher than 1 at all bias voltages. The asymmetric evolutions and alignment of the molecular orbitals with the applied bias were found to be essential for generating the molecular diode rectification behavior. Metal nature of metalloporphyrins and the interaction porphyrin-electrode significantly affect RR of molecular diode. Large metal ions like Cd(2+) and Ag(2+) in metalloporphyrins disfavor rectification creating conducting channels in two directions, while smaller ions Zn(2+) and Cu(2+) favor rectification increasing the interaction between gold electrode and porphyrin macrocycle.

Desulfurization of Model Gasoline by Adsorption Process with Ruthenium Ion Modified Y-Zeolites

Desulfurization of thiophene from model gasoline was carried out by using large charge number metal (Bi, Sb, Zr and Ru) ion modified NH4Y-zeolite by batch method. The sulfur uptake increased in the order of HY (0.85 mg/g) < BiY-1 (1.06 mg/g) < SbY-1(1.24 mg/g) < ZrY-1 (1.25 mg/g) < RuY-1 (1.35 mg/g). Sulfur uptake was influenced by Ru contentof RuY, which increased in the order of RuY-0.25 (1.11mg/g) < RuY-1 (1.41mg/g) < RuY-0.5 (1.68 mg/g). Sulfur removal was influenced by aromatics of model gasoline, i.e., sulfur removal of RuY-0.5 (42%) showed higher selectivity for thiophene than CeY-1 (24%) ones when model gasoline with toluene.

What a difference a carbon makes: H₄octapa vs H₄C3octapa, ligands for In-111 and Lu-177 radiochemistry.

The acyclic ligands H4C3octapa and p-SCN-Bn-H4C3octapa were synthesized for the first time, using nosyl protection chemistry. These new ligands were compared to the previously studied ligands H4octapa and p-SCN-Bn-H4octapa to determine the extent to which the addition of a single carbon atom to the backbone of the ligand would affect metal coordination, complex stability, and, ultimately, utility for in vivo radiopharmaceutical applications. Although only a single carbon atom was added to H4C3octapa and the metal donor atoms and denticity were not changed, the solution chemistry and radiochemistry properties were drastically altered, highlighting the importance of careful ligand design and radiometal–ligand matching. It was found that [In(C3octapa)]− and [Lu(C3octapa)]− were substantially different from the analogous H4octapa complexes, exhibiting fluxional isomerization and a higher number of isomers, as observed by 1H NMR, VT-NMR, and 2D COSY/HSQC-NMR experiments. Past evaluation of the DFT structures of [In(octapa)]− and [Lu(octapa)]− revealed very symmetric complexes; in contrast, the [In(C3octapa)]− and [Lu(C3octapa)]− complexes were much less symmetric, suggesting lower symmetry and less rigidity than that of the analogous H4octapa complexes. Potentiometric titrations revealed the formation constants (log KML, pM) were ∼2 units lower for the In3+ and Lu3+ complexes of H4C3octapa when compared to that of the more favorable H4octapa ligand (∼2 orders of magnitude less thermodynamically stable). The bifunctional ligands p-SCN-Bn-H4C3octapa and p-SCN-Bn-H4octapa were conjugated to the antibody trastuzumab and radiolabeled with 111In and 177Lu. Over a 5 day stability challenge experiment in blood serum, 111In-octapa– and 111In-C3octapa–trastuzumab immunoconjugates were determined to be ∼91 and ∼24% stable, respectively, and 177Lu-octapa– and 177Lu-C3octapa–trastuzumab, ∼89% and ∼4% stable, respectively. This work suggests that 5-membered chelate rings are superior to 6-membered chelate rings for large metal ions like In3+ and Lu3+, which is a crucial consideration for the design of bifunctional chelates for bioconjugation to targeting vectors for in vivo work.

Homo- and heterometallic luminescent 2-D stilbene metal–organic frameworks

Metal-organic frameworks (MOFs) can provide a matrix for the assembly of organic chromophores into well-defined geometries, allowing for tuning of the material properties and study of structure-property relationships. Here, we report on the effect of the coordinated metal ion on the luminescence properties of eight isostructural MOFs having the formula M(1)2M(2)L3(DMF)2 (M(1) = M(2) = Zn (1), Cd (2), Mn (3), Co (4); M(1) = Zn, M(2) = Cd (5), Mn (6), Co (7); M(1) = Co, M(2) = Mn (8); L = trans-4,4'-stilbene dicarboxylate), synthesized by reaction of the appropriate metal nitrate or mixtures of metal nitrates with LH2 in DMF. The crystal structures of 2, 3 and 5-8 were determined by X-ray diffraction to be composed of trinuclear metal clusters linked by stilbene dicarboxylate linkers in a paddlewheel geometry, extending to form a 2-D layered structure. In the mixed-metal cases, the larger metal ion was found to occupy the octahedral site in the cluster while the smaller ion occupies the tetrahedral positions, suggesting a selective, ligand-directed assembly process for the mixed-metal species. Variable temperature magnetic measurements for paramagnetic MOFs 3 and 6-8 were consistent with the site occupancies determined crystallographically, and indicated weak intra-cluster antiferromagnetic coupling for 3 and 8. Comparison between the crystal structures of 2, 3 and 5-8 and those reported for 1 and 4 in the literature reveal close resemblances between linker environments, with important intermolecular stilbene-stilbene geometries that are comparable in all cases. Interestingly, pale-colored 1-3 and 5-7 display very similar emission profiles upon excitation at λ(ex) = 350 nm, whereas dark-colored 4 and 8 do not exhibit detectable emission spectra. The bright, well-resolved luminescence of 1, 2 and 5 is ascribed to rigidification of the linker upon coordination to the d(10) metal ions, whereas the weaker emission observed for 3, 6 and 7 is presumably a result of quenching due to close proximity of the linker to one or more paramagnetic ions. Time-resolved measurements for 1, 2, 5 and 6 reveal biexponential emission decays, where the lifetime of the longer-lived state corresponds to observed variations in the nearest-neighbor cofacial stilbene-stilbene distances in their crystal structures. For 3, a monoexponential decay with shorter lifetime was determined, indicating significant paramagnetic quenching of its emissive state.

Synthesis and characterization of acid silver salts of 12-tungstophosphoric acid

The silver acid salts AgxH3−xPW12O40 (AgxWPA), where Ag content is x=1 up to x=2.5, were synthesized and characterized by Fourier transform infrared and micro-Raman spectroscopy, powder X-ray diffraction and differential thermal and thermogravimetric analysis and nitrogen adsorption. The properties of the prepared salts are compared with those of the parent acid. Regarding the structural, textural and thermal and solubility characteristics, these salts are between salts of group A, with small metal ions, and B group salts with large metal ions. The acid salts are two phase mixtures of soluble acid and insoluble neutral salt, like other alkaline acid salts of H3PW12O40 for x<2. The catalytic properties of the acid salts have been studied for the vapor-phase dehydration of ethanol, carried out in a conventional flow-type reactor at 300°C. The acid salts exhibited stable catalytic activity, a little bit lower than tungstophosphoric acid for ethylene production from ethanol.

Selective binding of antimicrobial porphyrins to the heme‐receptor IsdH‐NEAT3 of Staphylococcus aureus

The Isd (iron-regulated surface determinant) system of the human pathogen Staphylococcus aureus is responsible for the acquisition of heme from the host organism. We recently reported that the extracellular heme receptor IsdH-NEAT3 captures and transfers noniron antimicrobial porphyrins containing metals in oxidation state (III). However, it is unclear if geometric factors such as the size of the metal (ionic radius) affect binding and transfer of metalloporphyrins. We carried out an ample structural, functional, and thermodynamic analysis of the binding properties of antimicrobial indium(III)-porphyrin, which bears a much larger metal ion than the iron(III) of the natural ligand heme. The results demonstrate that the NEAT3 receptor recognizes the In(III)-containing PPIX in a manner very similar to that of heme. Site-directed mutagenesis identifies Tyr642 as the central element in the recognition mechanism as suggested from the crystal structures. Importantly, the NEAT3 receptor possesses the remarkable ability to capture dimers of metalloporphyrin. Molecular dynamics simulations reveal that IsdH-NEAT3 does not require conformational changes, or large rearrangements of the residues within its binding site, to accommodate the much larger (heme)2 ligand. We discuss the implications of these findings for the design of potent inhibitors against this family of key receptors of S. aureus.

Low temperature synthesis, photoluminescence, magnetic properties of the transition metal doped wurtzite ZnS nanowires

In this paper, we synthesized the transition metal ions (Mn, Cu, Fe) doped and co-doped ZnS nanowires (NWs) by a one-step hydrothermal method. The results showed that the solid solubility of the Fe2+ ions in the ZnS NWs was about two times larger than that of the Mn2+ or Cu2+ ions in the ZnS NWs. There was no phase transformation from hexagonal to cubic even in a large quantity transition metal ions introduced for all the samples. The Mn2+/Cu2+/Fe2+ related emission peaks can be observed in the Mn2+,Cu2+ and Fe2+ doped ZnS NWs. The ferromagnetic properties of the co-doped samples were investigated at room temperature.

Selectivity of the Highly Preorganized Tetradentate Ligand 2,9-Di(pyrid-2-yl)-1,10-phenanthroline for Metal Ions in Aqueous Solution, Including Lanthanide(III) Ions and the Uranyl(VI) Cation

Some metal ion complexing properties of DPP (2,9-Di(pyrid-2-yl)-1,10-phenanthroline) are reported with a variety of Ln(III) (Lanthanide(III)) ions and alkali earth metal ions, as well as the uranyl(VI) cation. The intense π-π* transitions in the absorption spectra of aqueous solutions of 10(-5) M DPP were monitored as a function of pH and metal ion concentration to determine formation constants of the alkali-earth metal ions and Ln(III) (Ln = lanthanide) ions. It was found that log K(1)(DPP) for the Ln(III) ions has a peak at Ln(III) = Sm(III) in a plot of log K(1) versus 1/r(+) (r(+) = ionic radius for 8-coordination). For Ln(III) ions larger than Sm(III), there is a steady rise in log K(1) from La(III) to Sm(III), while for Ln(III) ions smaller than Sm(III), log K(1) decreases slightly to the smallest Ln(III) ion, Lu(III). This pattern of variation of log K(1) with varying size of Ln(III) ion was analyzed using MM (molecular mechanics) and DFT (density functional theory) calculations. Values of strain energy (∑U) were calculated for the [Ln(DPP)(H(2)O)(5)](3+) and [Ln(qpy)(H(2)O)(5)](3+) (qpy = quaterpyrdine) complexes of all the Ln(III) ions. The ideal M-N bond lengths used for the Ln(III) ions were the average of those found in the CSD (Cambridge Structural Database) for the complexes of each of the Ln(III) ions with polypyridyl ligands. Similarly, the ideal M-O bond lengths were those for complexes of the Ln(III) ions with coordinated aqua ligands in the CSD. The MM calculations suggested that in a plot of ∑U versus ideal M-N length, a minimum in ∑U occurred at Pm(III), adjacent in the series to Sm(III). The significance of this result is that (1) MM calculations suggest that a similar metal ion size preference will occur for all polypyridyl-type ligands, including those containing triazine groups, that are being developed as solvent extractants in the separation of Am(III) and Ln(III) ions in the treatment of nuclear waste, and (2) Am(III) is very close in M-N bond lengths to Pm(III), so that an important aspect of the selectivity of polypyridyl type ligands for Am(III) will depend on the above metal ion size-based selectivity. The selectivity patterns of DPP with the alkali-earth metal ions shows a similar preference for Ca(II), which has the most appropriate M-N lengths. The structures of DPP complexes of Zn(II) and Bi(III), as representative of a small and of a large metal ion respectively, are reported. [Zn(DPP)(2)](ClO(4))(2) (triclinic, P1, R = 0.0507) has a six-coordinate Zn(II), with each of the two DPP ligands having one noncoordinated pyridyl group appearing to be π-stacked on the central aromatic ring of the other DPP ligand. [Bi(DPP)(H(2)O)(2)(ClO(4))(2)](ClO(4)) (triclinic, P1, R = 0.0709) has an eight-coordinate Bi, with the coordination sphere composed of the four N donors of the DPP ligand, two coordinated water molecules, and the O donors of two unidentate perchlorates. As is usually the case with Bi(III), there is a gap in the coordination sphere that appears to be the position of a lone pair of electrons on the other side of the Bi from the DPP ligand. The Bi-L bonds become relatively longer as one moves from the side of the Bi containg the DPP to the side where the lone pair is thought to be situated. A DFT analysis of [Ln(tpy)(H(2)O)(n)](3+) and [Ln(DPP)(H(2)O)(5)](3+) complexes is reported. The structures predicted by DFT are shown to match very well with the literature crystal structures for the [Ln(tpy)(H(2)O)(n)](3+) with Ln = La and n = 6, and Ln = Lu with n = 5. This then gives one confidence that the structures for the DPP complexes generated by DFT are accurate. The structures generated by DFT for the [Ln(DPP)(H(2)O)(5)](3+) complexes are shown to agree very well with those generated by MM, giving one confidence in the accuracy of the latter. An analysis of the DFT and MM structures shows the decreasing O--O nonbonded distances as one progresses from La to Lu, with these distances being much less than the sum of the van der Waals radii for the smaller Ln(III) ions. The effect that such short O--O nonbonded distances has on thermodynamic complex stability and coordination number is then discussed.

Production and characterization of the celery mismatch endonuclease CEL II using baculovirus/silkworm expression system

Mutation and polymorphism detection by nucleases has become a more important tool in clinical and biological researches. There are several kinds of single-stranded nucleases for detecting mismatched DNAs. One of them, CEL II, was isolated from Apium graveolens and cleaves DNA with high specificity at sites of mismatch. High-throughput mutation scanning requires large quantity of CEL II endonuclease. Here, we demonstrate high-level expression of CEL II using silkworm-baculovirus system. The recombinant CEL II secreted in silkworm hemolymph was glycosylated and susceptible to N-glycosidase F. Additionally, larger metal ions such as Ca(2+) and Sr(2+) were able to replace Mg(2+) and enhanced mismatch cleavage activity of CEL II. These results indicate that the silkworm-baculovirus platform is a good alternative system to obtain the functional CEL II.

Smaragdyrins: Emeralds of Expanded Porphyrin Family

Porphyrins are tetrapyrrolic 18 π electron conjugated macrocycles with wide applications that range from materials to medicine. Expanded porphyrins, synthetic analogues of porphyrins that contain more than 18 π electrons in the conjugated pathway, have an increased number of pyrroles or other heterocyles or multiple meso-carbon bridges. The expanded porphyrins have attracted tremendous attention because of unique features such as anion binding or transport that are not present in porphyrins. Expanded porphyrins exhibit wide applications that include their use in the coordination of large metal ions, as contrasting agents in magnetic resonance imaging (MRI), as sensitizers for photodynamic therapy (PDT) and as materials for nonlinear optical (NLO) studies. Pentaphyrin 1, sapphyrin 2, and smaragdyrin 3 are expanded porphyrins that include five pyrroles or heterocyclic rings. They differ from each other in the number of bridging carbons and direct bonds that connect the five heterocyclic rings. Sapphyrins were the first stable expanded porphyrins reported in the literature and remain one of the most extensively studied macrocycles. The strategies used to synthesize sapphyrins are well established, and these macrocycles are versatile anion binding agents. They possess rich porphyrin-like coordination chemistry and have been used in diverse applications. This Account reviews developments in smaragdyrin chemistry. Although smaragdyrins were discovered at the same time as sapphyrins, the chemistry of smaragdyrins remained underdeveloped because of synthetic difficulties and their comparative instability. Earlier efforts resulted in the isolation of stable β-substituted smaragdyrins and meso-aryl isosmaragdyrins. Recently, researchers have synthesized stable meso-aryl smaragdyrins by [3 + 2] oxidative coupling reactions. These results have stimulated renewed research interest in the exploration of these compounds for anion and cation binding, energy transfer, fluorescent sensors, and their NLO properties. Recently reported results on smaragdyrin macrocycles have set the stage for further synthetic studies to produce stable meso-aryl smaragdyrins with different inner cores to study their properties and potential for various applications.

The overhanging carboxylic acid strategy: an alternative route to the porphyrin core expansion/modification for the coordination of large metal ions

This account summarizes how the binding properties of a regular porphyrin macrocycle for large cations can be significantly modified and even tuned when the surrounding skeleton delivers at least one carboxylic acid group close to the N -core. While kinetics of metal insertion are drastically improved, unique dinuclear species can be obtained with a possible control of the nuclearity. The first incorporation of an α-core emitter radioisotope of particular interest for cancer therapy was recently demonstrated. All in all, this overhanging carboxylic acid strategy can be regarded as an alternative to either expanded porphyrins for the coordination of large cations from groups 14–15 (PbII, BiIII) or contracted and isomeric porphyrins for the coordination of smaller cations from group 12 (HgII)

Metal-Ion-Complexing Properties of 2-(Pyrid-2′-yl)-1,10-phenanthroline, a More Preorganized Analogue of Terpyridyl. A Crystallographic, Fluorescence, and Thermodynamic Study

Some metal-ion-complexing properties of the ligand 2-(pyrid-2'-yl)-1,10-phenanthroline (MPP) are reported. MPP is of interest in that it is a more preorganized version of 2,2';6,2''-terpyridine (tpy). Protonation constants (pK(1) = 4.60; pK(2) = 3.35) for MPP were determined by monitoring the intense π-π* transitions of 2 × 10(-5) M solutions of the ligand as a function of the pH at an ionic strength of 0 and 25 °C. Formation constants (log K(1)) at an ionic strength of 0 and 25 °C were obtained by monitoring the π-π* transitions of MPP titrated with solutions of the metal ion, or 1:1 solutions of MPP and the metal ion were titrated with acid. Large metal ions such as Ca(II) or La(III) showed increases of log K(1) of about 1.5 log units compared to that of tpy. Small metal ions such as Zn(II) and Ni(II) showed little increase in log K(1) for MPP compared to the tpy complexes, which is attributed to the presence of five-membered chelate rings in the MPP complexes, which favor large metal ions. The structure of [Cd(MPP)(H(2)O)(NO(3))(2)] (1) is reported: monoclinic, P2(1)/c, a = 7.4940(13) Å, b = 12.165(2) Å, c = 20.557(4) Å, β = 96.271(7)°, V = 1864.67(9) Å(3), Z = 4, and final R = 0.0786. The Cd in 1 is seven-coordinate, comprising the three donor atoms of MPP, a coordinated water, a monodentate, and a bidentate NO(3)(-). Cd(II) is a fairly large metal ion, with r(+) = 0.96 Å, slightly too small for coordination with MPP. The effect of this size matching in terms of the structure is discussed. Fluorescence spectra of 2 × 10(-7) M MPP in aqueous solution are reported. The nonprotonated MPP ligand fluoresces only weakly, which is attributed to a photoinduced-electron-transfer effect. The chelation-enhanced-fluorescence (CHEF) effect induced by some metal ions is presented, and the trend of the CHEF effect, which is Ca(II) > Zn(II) > Cd(II) ~ La(III) > Hg(II), is discussed in terms of factors that control the CHEF effect, such as the heavy-atom effect.

Surface Measurement of GLSI Wafer with Copper Interconnects after CMP

Chemical mechanical polishing (CMP) is the best global planarization technology of GLSI process. After CMP process, there may appear large roughness, micro scratch, dishing pit, erosion pit, with-in-wafer-non-uniformity (WIWNU), organic contamination, particles and metal ions pollution on wafer with copper interconnects. Surface measurement of CMP process on the wafer mainly involves the test of roughness, defects and the contaminations. Atomic force profiler (AFP) combined with the resolution of the AFM and long-range-scan ability of the steps instrument (100 mm), is suitable for CMP process which needs to measure both the planarization of long-range scanning and tungsten plug and copper interconnects with high resolution imaging. Optical detection technology combined with the advantages of dark and bright view detection is suitable for detection of particles, crystal originated pits (COP), defects, etc. The time-of-flight static secondary ion mass spectrometry (TOF-SIMS) and total reflection X-ray fluorescence (TXRF) are applicable to detect metal ions. The selection and use of advanced data analysis theory and method can help to improve the speed of analysis and to find the main factors of influence surface quality. Pareto diagram analysis is very beneficial for study polishing effects and the main reason of the surface state for Cu-CMP wafer. Nine sampling method and five sampling method fit to analysis the uniform surface distribution, on the contrast isometric sampling can reflect the distribution of the surface state along the radius difference.

Adsorption of Cu(II), Ni(II), Zn(II), Cd(II) and Pb(II) onto Kaolin/Zeolite Based- Geopolymers

This work deals with geopolymers based on local Jordanian resources, namely, kaolin and zeoltitic (phillipsite) tuff. The geopolymers were prepared from these two materials by a reaction with an alkali solution at 80oC. The research group of the present work has demonstrated in previous work that addition of zeolitic tuff to kaolin based-geopolymers increases the adsorption capacity toward Cu(II) metal ion compared to zeolite-free geopolymers, while retaining high mechanical strength. The aim of the present work is to extend our work and to study the effect of changing geopolymers components (zeolitic tuff and kaolin) on their adsorption properties toward Cu(II), Ni(II), Zn(II), Cd(II) and Pb(II) metal ions. Both isothermal and kinetic studies revealed that increasing the zeolitic tuff: kaolin ratio improves the adsorption capacity of geopolymer toward metal ions. The adsorption capacity of the geopolymers of 150: 50 zeolites: kaolin content was found to be higher than that of the raw materials themselves. The rate of adsorption of geopolymers was found to be lower than that of raw materials due to kinetic limitations imposed by the formation of geopolymerization network. The selectivity of geopolymers toward adsorption of metal ions was found to be distinct from raw zeolite and kaolin where the adsorption onto geopolymers was found to be more preferential for small size metal ions (Cu(II), Ni(II), Zn(II)) than for large size metal ions (Pb(II), Cd(II)). The adsorption of Cu(II) and Pb(II) onto geopolymers did not decrease with competition with other metal ions, which indicates cooperative adsorption. The adsorption process of metal ions onto geopolymers was found to be reversible that indicates that metal ions are bound by physical cation exchange to the exchangeable sites of unreacted phillipsite and new amorphous geopolymer sites. Leaching of metal ions from raw kaolin was much more effective than geopolymers and zeolite because of compact structure of geopolymers.

Effect of ionic radius on the assemblies of first row transition metal–5-tert-butylisophthalates–(2,2′-bipyridine or phenanthroline) coordination compounds

18 coordination compounds of Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+, with mixed organic ligands 5-tert-butylisophthalic acid, 2,2′-bipyridine or phenanthroline, have been hydrothermally synthesized and characterized. Structure analysis shows that the ionic radius of a metal ion determines the form of the metal centre and the structure of the product. Large metal ions tend to have higher coordination numbers, connect to more bridging ligands and form multinuclear metal centres. On the contrary, small metal ions tend to connect to fewer bridging ligands, and act as mononuclear metal centres for discrete coordination compounds or low dimensional coordination polymers. The influences of other factors such as molar ratio of reactants, pH and temperature, have also been discussed. The magnetic properties of the temperature dependent cobalt compounds have been investigated.

Alkali Metal/Lanthanoid Heterobimetallic Complexes of 8‐Hydroxyquinolines Accessed by Pseudo‐Solid‐State Reactions

AbstractThe heterobimetallic 1D‐polymeric alkali metal/lanthanoid [AMLn(Q)4]n [Q = OQ (8‐quinolinolate): AM = Li, Ln = Tb, Ho, Er; AM = K, Ln = Er; Q = MQ (2‐methyl‐8‐quinolinolate): AM = Rb; Ln = Tb, Er] complexes were obtained after rearrangement reactions between AM(Q) and Ln(Q)3 in a 1,2,4,5‐tetramethylbenzene flux at elevated temperatures. In these compounds, the eight‐coordinate lanthanoid ion is surrounded by four (O, N) chelating Q ligands, which bridge to the adjacent alkali metal through their oxygen atoms to form the linear polymers. Dimeric [Cs2(MQ)2(HMQ)2] was obtained from an attempt to prepare [CsEr(MQ)4]n, and the caesium atoms are each ligated by one terminal HMQ and one chelating‐bridging MQ ligand. In addition, the chelating‐bridging ligands in [Cs2(MQ)2(HMQ)2] and in the rubidium derivatives [RbLn(MQ)4]n (Ln = Tb, Er) exhibit bonding of the π‐electron system to coordination saturate the large ionic alkali metal ion. The reaction of Yb(MQ)3 in the presence of K2C2O4·H2O afforded the monomeric heterobimetallic [KYb2(MQ)7] complex in which the three metal atoms are arranged in a triangular fashion. They are surrounded by seven MQ ligands, which display the previously encountered chelating (O, N) and the chelating‐bridging μ‐κ2(N,O):κ1(O) and μ3‐κ2(N,O):κ1(O):κ1(O) ligation modes. Heating K(OQ) in 1,2,3,4‐tetrachlorobenzene gave crystals of 8‐hydroxyquinolinium chloride. The structure of [Na4(OQ)4(H2O)8]n, obtained by neutralisation, has sodium ions coordinated by one chelating OQ and four aqua ligands, the latter bridge to adjacent sodium ions to give a double stranded 2D‐polymer.

Unusual Metal Ion Selectivities of the Highly Preorganized Tetradentrate Ligand 1,10-Phenanthroline-2,9-dicarboxamide: A Thermodynamic and Fluorescence Study

Some metal ion complexing properties of the ligand PDAM (1,10-phenanthroline-2,9-dicarboxamide) in aqueous solution are reported. Using UV-visible spectroscopy to follow the intense π-π* transitions of PDAM as a function of metal ion concentration, log K(1) values in 0.1 M NaClO(4) and at 25 °C are, for Cu(II), 3.56(5); Ni(II), 3.06(5); Zn(II), 3.77(5); Co(II), 3.8(1); Mg(II), 0.1(1); Ca(II), 1.94(4); and Ba(II), 0.7(1). For more strongly bound metal ions, competition reactions between PDAM and EDTA (ethylenedinitrilo-tetraacetic acid) or tetren (1,4,7,10,13-pentaazatridecane), monitored following the UV spectrum of PDAM, gave the following log K(1) values in 0.1 M NaClO(4) and at 25 °C: Cd(II), 7.1(1); Pb(II), 5.82(5); In(III), 9.4(1); and Bi(III), 9.4(1). The very low log K(1)(PDAM) values for small metal ions such as Cu(II) or Zn(II) are unprecedented for a phen-based ligand (phen = 1,10-phenanthroline), which is rationalized in terms of the low basicity of the N donors of the ligand (pK(a) = 0.6) and the fact that PDAM has a best-fit size corresponding to large metal ions of ionic radius ~1.0 Å. Large metal ions with ionic radius ≥1.0 Å show large increases in log K(1) relative to their phen complexes, which in turn produces unparalleled selectivities, such as a 3.5 log units greater log K(1)(PDAM) for Cd(II) than for Cu(II). PDAM shows strong fluorescence in aqueous solution, suggesting that its carboxamide groups do not produce a fluorescence-quenching photon-induced electron transfer (PET) effect. Only Ca(II) produces a weak CHEF (chelation enhanced fluorescence) effect with PDAM, while all other metal ions tested produce a decrease in fluorescence, a CHEQ (chelation enhanced quenching effect). The production of the CHEQ effect is rationalized in terms of the idea that coordination of metal ions to PDAM stabilizes a canonical form of the carboxamide groups that promotes a PET effect.

Sandalwood Fragrance Biosynthesis Involves Sesquiterpene Synthases of Both the Terpene Synthase (TPS)-a and TPS-b Subfamilies, including Santalene Synthases

Sandalwood oil is one of the worlds most highly prized fragrances. To identify the genes and encoded enzymes responsible for santalene biosynthesis, we cloned and characterized three orthologous terpene synthase (TPS) genes SaSSy, SauSSy, and SspiSSy from three divergent sandalwood species; Santalum album, S. austrocaledonicum, and S. spicatum, respectively. The encoded enzymes catalyze the formation of α-, β-, epi-β-santalene, and α-exo-bergamotene from (E,E)-farnesyl diphosphate (E,E-FPP). Recombinant SaSSy was additionally tested with (Z,Z)-farnesyl diphosphate (Z,Z-FPP) and remarkably, found to produce a mixture of α-endo-bergamotene, α-santalene, (Z)-β-farnesene, epi-β-santalene, and β-santalene. Additional cDNAs that encode bisabolene/bisabolol synthases were also cloned and functionally characterized from these three species. Both the santalene synthases and the bisabolene/bisabolol synthases reside in the TPS-b phylogenetic clade, which is more commonly associated with angiosperm monoterpene synthases. An orthologous set of TPS-a synthases responsible for formation of macrocyclic and bicyclic sesquiterpenes were characterized. Strict functionality and limited sequence divergence in the santalene and bisabolene synthases are in contrast to the TPS-a synthases, suggesting these compounds have played a significant role in the evolution of the Santalum genus.