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51.
Arnold PL Edworthy IS Carmichael CD Blake AJ Wilson C 《Dalton transactions (Cambridge, England : 2003)》2008,(28):3739-3746
Magnesium dications bind strongly to a tridentate anionic dicarbene ligand L = [N{CH(2)CH(2)(CNCHCHNMes)}(2)] forming dinuclear and trinuclear Mg complexes with some particularly short Mg-C bonds. Treatment of the proligand H(4)LCl(3) with three equivalents of methyl magnesium chloride or benzyl magnesium chloride affords Mg(3)(HL)Cl(6) in high yield. A suspension of in thf was heated to 80 degrees C for 2 h to afford Mg(2)(L)Cl(3), consistent with the loss of one equivalent of MgCl(2), and the deprotonation of the remaining acidic NH, lost as HCl gas. Treatment of Mg(3)(HL)Cl(6) with one equivalent of KC(8) results in deprotonation of the ligand amine NH to afford Mg(3)(L)Cl(5); treatment with a second equivalent forms the radical anion of the complex, K[Mg(3)(L)Cl(5)], which decomposes upon storage, precluding its structural characterisation. The acidic NH proton of the ligand in Mg(3)(HL)Cl(6) can also be removed by deprotonation with Li{N(SiMe(3))(2)}; additional equivalents of which also exchange the magnesium-bound chlorides for silylamido ligands, affording Mg(2)(L)Cl(2)N' and Mg(2)(L)Cl(N')(2), which have both been characterised by single-crystal X-ray diffraction studies. 相似文献
52.
Synthetic mimics of mammalian cell surface receptors: prosthetic molecules that augment living cells
Peterson BR 《Organic & biomolecular chemistry》2005,3(20):3607-3612
Specific receptors on the surface of mammalian cells actively internalize cell-impermeable ligands by receptor-mediated endocytosis. To mimic these internalizing receptors, my laboratory is studying artificial cell surface receptors that comprise N-alkyl derivatives of 3beta-cholesterylamine linked to motifs that bind cell-impermeable ligands. When added to living mammalian cells, these synthetic receptors insert into cellular plasma membranes, project ligand-binding small molecules or peptides from the cell surface, and enable living cells to internalize targeted proteins and other cell-impermeable compounds. These artificial receptors mimic their natural counterparts by rapidly cycling between plasma membranes and intracellular endosomes, associating with proposed cholesterol and sphingolipid-rich lipid raft membrane microdomains, and delivering ligands to late endosomes/lysosomes. This "synthetic receptor targeting" strategy is briefly reviewed here and contrasted with other related cellular delivery systems. Potential applications of artificial cell surface receptors as molecular probes, agents for cellular targeting, tools for drug delivery, and methods for ligand depletion are discussed. The construction of synthetic receptors as prosthetic molecules, designed to seamlessly augment the molecular machinery of living cells, represents an exciting new frontier in the fields of bioorganic chemistry and chemical biology. 相似文献
53.
Huygens D Boeckx P Vermeulen J Paepe XD Park A Barker S Pullan C Van Cleemput O 《Rapid communications in mass spectrometry : RCM》2005,19(22):3232-3238
A new method has been developed to analyse 15N of the total dissolved nitrogen (TDN) pool. The method operates on a commercial total organic carbon (TOC) analyser coupled to an elemental analyser/isotope ratio mass spectrometer (EA-IRMS). Nitrogen compounds are combusted to nitric oxide (NO) and nitrogen dioxide (NO2) by high-temperature catalytic oxidation (HTCO), after which the NOx gas is transferred to an EA-IRMS for isotopic nitrogen analysis. The system is described, including five modifications of the system in order to overcome analytical problems. First, flow paths were modified to run both systems on helium as carrier gas, while complete sample oxidation was maintained. Secondly, the catalyst structure was adapted to allow high injection volumes at the given backpressures delivered by the EA system. Thirdly, we installed a Permapure dehumidification system as the standard Peltier element did not satisfy dehumidification requirements. Finally, we prevented the inflow of atmospheric nitrogen into the system. In a final stage, we are planning to automate the coupled system in order to run a continuous batch of up to 60 samples. We have obtained satisfactory results on the accuracy and precision of 180+/-1 per thousand potassium nitrate samples (IAEA, USGS-32). Running a batch of five samples resulted in a mean isotopic value of 178.8 per thousand with a standard deviation of 2.8 per thousand. Some important issues could not yet be addressed here, and will have to be evaluated once the system is running on a continuous base. However, the results appear promising and this system has the potential to become a method for TD15N analysis. An appropriate TD15N analysis method might open new challenges in aquatic and terrestrial ecosystem nitrogen studies, including a more comprehensive study of the dissolved organic nitrogen pool. 相似文献
54.
55.
Ibarra IA Yang S Lin X Blake AJ Rizkallah PJ Nowell H Allan DR Champness NR Hubberstey P Schröder M 《Chemical communications (Cambridge, England)》2011,47(29):8304-8306
The metal-organic frameworks NOTT-400 and NOTT-401, based on a binuclear [Sc(2)(μ(2)-OH)(O(2)CR)(4)] building block, have been synthesised and characterised; the desolvated framework NOTT-401a shows a BET surface area of 1514 m(2) g(-1) with a total H(2) uptake of 4.44 wt% at 77 K and 20 bar. 相似文献
56.
Wenzel AG Blake G VanderVelde DG Grubbs RH 《Journal of the American Chemical Society》2011,133(16):6429-6439
The reaction of the phosphonium alkylidene [(H(2)IMes)RuCl(2)=CHP(Cy)(3))](+) BF(4)(-) with propene, 1-butene, and 1-hexene at -45 °C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of α-monosubstituted and α,α'-disubstituted (both cis and trans) ruthenacycles. On an NMR time scale, rapid chemical exchange was found to preferentially occur between the β-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR time scale was also observed between the α- and β-methylene groups of the monosubstituted ruthenacycle (H(2)IMes)Cl(2)Ru(CHRCH(2)CH(2)) (R = CH(3), CH(2)CH(3), (CH(2))(3)CH(3)). EXSY NMR experiments at -87 °C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analogue. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H(2)IMes)Cl(2)Ru(CH(2)CH(2)CH(2)) was observed in up to 98% yield via NMR at -40 °C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics toward olefin metathesis catalyst and reaction design are described. 相似文献
57.
58.
Dan M.J. Doble Richard D. Kay Colin H. Benison Alexander J. Blake Xiang Lin Claire Wilson Martin Schröder 《Journal of inclusion phenomena and macrocyclic chemistry》2001,41(1-4):23-30
Reaction of tris-(2-aminoethyl)amine (tren) andthe sodium salt of an -ketocarboxylic acid, typically sodium pyruvate, affordsin the presence of a lanthanide ion aseries of complexes and aggregates includingmononuclear, cyclic tetranuclear and polymerspecies of [L1]3- ([L1]3-=N[CH2CH2N=C(CH3)COO-]3).The aggregation of these and related d-block elementcomplexes with Na+ ions leadsto the formation of polymeric materials, and thefactors influencing the formation and controlof these various aggregation states are discussed.Metal cations also template the aggregationof the fragment [Ni(L2)] ([L2]2- =CH2[CH2N = C(CH3)COO-]2)to give, in high yield, the polynuclearaggregates {[Ni(L2)]6M}x+(M = Nd, Pr, Ce, La, x = 3; M = Sr, Ba, x = 2). The structures of{[Ni(L2)]6M}x+ show aninterstitial twelve co-ordinate, icosahedralcation Mx+ encapsulated by six [Ni(L2)]fragments. In the presence ofNa+, aggregation of [Ni(L2)] fragments affords {[Ni(L2)]9Na4(H2O)(MeOH)(ClO4)}3+ thestructure of whichshows four Na+ ions templating the formation ofa distorted tricapped trigonal prismatic[Ni(L2)]9 cage. Thus, control overconstruction of various polynuclear cages viaself-assembly at octahedral junctions can beachieved using main group, transition metaland lanthanide ion templates. 相似文献
59.
Tan WG Carnelley TJ Murphy P Wang H Lee J Barker S Weinfeld M Le XC 《Journal of chromatography. A》2001,924(1-2):377-386
Detection of benzo[a]pyrene diol epoxide (BPDE)-damaged DNA in a human lung carcinoma cell line (A549) has been performed using free zone affinity capillary electrophoresis with laser-induced fluorescence (LIF). Using BPDE as a model carcinogenic compound, the speed, sensitivity and specificity of this technique was demonstrated. Under free zone conditions, an antibody bound adduct was baseline-resolved from an unbound adduct in less than 2 min. The efficiencies of separation were in excess of 6 x 10(5) and 1 x 10(6) plates per meter for the antibody-bound and unbound adducts, respectively. Separation using a low ionic strength buffer permitted the use of a high electric field (830 V/cm) without the loss of resolving power. Using LIF detection, a concentration detection limit of roughly 3 x 10(-10) M was achieved for a 90-mer oligonuleotide containing a single BDPE. The use of formamide in the incubation buffer to enhance denaturing of DNA did not affect the stability of the complex between the antibody and the adducts. Using a fluorescently labeled BPDE-modified DNA adduct probe, a competitive assay was established to determine the levels of BPDE-DNA adducts in A549 cells. 相似文献
60.
Blake AJ Brett MT Champness NR Khlobystov AN Long DL Wilson C Schröder M 《Chemical communications (Cambridge, England)》2001,(21):2258-2259
4,4'-Bipyridine N,N'-dioxide (L) acts as a hydrogen-bond acceptor in the compounds ([M(NO3)2(H2O)4].L2) (M = Co, Ni) to form doubly-interpenetrated framework materials with sixfold topological connectivity. 相似文献