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361.
Alla Dolgopolova Dominik J. Weiss Reimar Seltmann Chris Stanley Barry Coles Andriy K. Cheburkin 《International journal of environmental analytical chemistry》2013,93(12):889-899
A reliable and robust procedure using closed-vessel microwave digestion of lichens and leaves for precise and accurate determination of trace elements (Pb, Zn and Cu) and stable Pb isotope ratios is presented. The method was developed using certified reference material CRM 482 Pseudovernia furfurea (Lichens), NIST 1515 (Apple Leaves) and NIST 1547 (Peach Leaves) and tested on lichens from a mining site in Russia. A mixture of 3?mL of HNO3, 3?mL of H2O2, 2?mL of H2O and 0.8?mL of HF ensured complete sample dissolution with 100?±?5% recovery for Pb, Zn and Cu at a maximum temperature of 210°C and pressure of 350?psi. The amount of HF and microwave pressure significantly influenced Pb, Zn and Cu recovery. Comparison between EMMA-XRF and ICP-AES showed a good correlation between Pb, Zn and Cu concentrations. Using the newly developed digestion method, Pb isotopes in lichens from the mining site were determined with an internal precision better than 0.02%. 相似文献
362.
Dr. Amanda J Welford Dr. John J. Caldwell Dr. Manjuan Liu Meirion Richards Dr. Nathan Brown Dr. Cara Lomas Dr. Graham J. Tizzard Dr. Mateusz B. Pitak Dr. Simon J. Coles Prof. Suzanne A. Eccles Dr. Florence I. Raynaud Prof. Ian Collins 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5657-5664
The 2,11‐cembranoid family of natural products has been used as inspiration for the synthesis of a structurally simplified, functionally diverse library of octahydroisobenzofuran‐based compounds designed to augment a typical medicinal chemistry library screen. Ring‐closing metathesis, lactonisation and SmI2‐mediated methods were exemplified and applied to the installation of a third ring to mimic the nine‐membered ring of the 2,11‐cembranoids. The library was assessed for aqueous solubility and permeability, with a chemical‐space analysis performed for comparison to the family of cembranoid natural products and a sample set of a screening library. Preliminary investigations in cancer cells showed that the simpler scaffolds could recapitulate the reported anti‐migratory activity of the natural products. 相似文献
363.
Mansfield NE Coles MP Hitchcock PB 《Dalton transactions (Cambridge, England : 2003)》2005,(17):2833-2841
Diisopropylcarbodiimide, (i)PrN[double bond, length as m-dash]C[double bond, length as m-dash]N(i)Pr, inserts into the lithium-phosphorus bond of in situ prepared "Ph(2)PLi(THF)(n)" to afford the lithium salt, [Li(Ph(2)PC{N(i)Pr}(2))(THF)(n)](x)(2a); alternatively, this compound can be made by deprotonation of the neutral phosphaguanidine, Ph(2)PC{N(i)Pr}{NH(i)Pr}(1a) with (n)BuLi. Displacement of the THF solvate in 2a is readily achieved with TMEDA to afford Li(Ph(2)PC{N(i)Pr}(2))(TMEDA)(3a). X-Ray crystallographic analyses show that 2a exists as a dimer in the solid state with a folded ladder structure and an N,N' chelating phosphaguanidinate, while 3a is monomeric with N,P-coordination of the ligand to lithium. Compound 2a reacts via a transmetallation pathway with AlMe(2)Cl to afford the dimethylaluminium complex, Al(Ph(2)PC{N(i)Pr}(2))Me(2)(4a), which can also be prepared by protonation of a methyl group of AlMe(3) using 1a. The formation of a series of dialkylaluminium compounds has been investigated employing this latter pathway using both 1a and the N,N'-dicyclohexyl analogue, Ph(2)PC{NCy}{NHCy}(1b), affording Al(Ph(2)PC{NR}(2))Et(2)(5a,b), Al(Ph(2)PC{NR}(2))(i)Bu(2)(6a,b) and the diphenylaluminium compound Al(Ph(2)PC{N(i)Pr}(2))Ph(2)(7a). The oily nature of most of the dialkyl compounds and high sensitivity to oxygen and moisture lead to difficulty in manipulation and characterization; however, NMR spectroscopy indicated highly pure products (>95%) upon removal of the solvent. The molecular structures of the crystalline examples 4a and 7a are reported, showing monomeric aluminium species with symmetrically chelating phosphaguanidinate ligands. The series of aluminium compounds AlLCl(2){L=[EC{NiPr}(2)](-): A, E=Me; B, E=Me(2)N; C, E=(Me(3)Si)(2)N and D, E=Ph(2)P} were investigated using density functional theory. In the more simple cases A and B, the delocalized electron density of the metallacycle was represented by a combination of the HOMO and an orbital of lower energy (A, HOMO-5; B, HOMO-6). The HOMO-1 in B was pi-bonded across the Me(2)N-C bond suggesting delocalization of electron density into the metallacycle. In the more complex systems C and D, delocalization within the metallacycle was less extensive due to the (Me(3)Si)(2)N- and Ph(2)P-moieties. A number of occupied orbitals in D, however, display phosphorus 'lone-pair' characteristics, indicating that these species have the potential to behave as Lewis bases in the formation of poly(metallic) systems. 相似文献
364.
Aaron J. Scott Julia Vallejo Arup Sarkar Lucy Smythe E. Regincs Martí Gary S. Nichol Wim T. Klooster Simon J. Coles Mark Murrie Gopalan Rajaraman Stergios Piligkos Paul J. Lusby Euan K. Brechin 《Chemical science》2021,12(14):5134
Reaction of Ni(OTf)2 with the bisbidentate quaterpyridine ligand L results in the self-assembly of a tetrahedral, paramagnetic cage [NiII4L6]8+. By selectively exchanging the bound triflate from [OTf⊂NiII4L6](OTf)7 (1), we have been able to prepare a series of host–guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MIIX4⊂NiII4L6](OTf)6, where MIIX42− = MnCl42− (2), CoCl42− (5), CoBr42− (6), NiCl42− (7), and CuBr42− (8) or [MIIIX4⊂NiII4L6](OTf)7, where MIIIX4− = FeCl4− (3) and FeBr4− (4). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations. Host–guest complexes 1–8 all crystallise as homochiral racemates in monoclinic space groups, wherein the four {NiN6} vertexes within a single Ni4L6 unit possess the same Δ or Λ stereochemistry. Magnetic susceptibility and magnetisation data show that the magnetic exchange between metal ions in the host [NiII4] complex, and between the host and the MX4n− guest, are of comparable magnitude and antiferromagnetic in nature. Theoretically derived values for the magnetic exchange are in close agreement with experiment, revealing that large spin densities on the electronegative X-atoms of particular MX4n− guest molecules lead to stronger host–guest magnetic exchange interactions.The tetrahedral [NiII4L6]8+ cage can reversibly bind paramagnetic MX41/2− guests, inducing magnetic exchange interactions between host and guest. 相似文献