Polymer imprinting with iron-oxo-hydroxo clusters: [Fe6O2(OH)2(O2CC(Cl)=CH2)12(H2O)2], [Fe6O2(OH)2(O2C-Ph-(CH)=CH2)12(H2O)2] and [{Fe(O2CC(Cl)=CH2)(OMe)2}10].

We report the syntheses of imprinted polymers using iron-oxo-hydroxo clusters as templates. Three new iron clusters, [Fe(6)O(2)(OH)(2)(O(2)CC(Cl)=CH(2))(12)(H(2)O)(2)] (1), [{Fe(O(2)CC(Cl)=CH(2))(OMe)(2)}(10)] (2) and [Fe(6)O(2)(OH)(2)(O(2)C-Ph-(CH)=CH(2))(12)(H(2)O)(2)] (3) have been prepared from commercially-available carboxylic acids. Cluster-imprinted-polymers (CIPs) of 1, 2 and 3 were prepared with ethylene glycol dimethacrylate monomer, and of 1 with methyl methacrylate monomer.

Di-, tri-, and tetranuclear zinc hydroxamate complexes as structural models for the inhibition of zinc hydrolases by hydroxamic acids.

Attempts to produce Zn analogues of the structural model complexes [M2(mu-O2CR)2(O2CR)2(mu-H2O)(tmen)2] (M = Ni, Co, Mn; R = CH(3), C(CH3)3, CF3) by the reaction of a series of zinc carboxylates with N,N,N',N'-tetramethylethylenediamine (tmen), resulted in the mononuclear complexes [Zn(OAc)(2)(tmen)] (1) and [Zn(crot)2(tmen)].(0.5)H2O (2) for R = CH3 and (CH)2CH3, respectively, and the dinuclear complexes [Zn(2)(mu-piv)(2)(piv)(2)(mu-H2O)(tmen)2] (3) and [Zn2(mu-OAc(F))2(OAc(F))2(mu-H2O)(tmen)2] (4) for R = C(CH3)3 and CF3, respectively.

A DFT study of model complexes of zinc hydrolases and their inhibition by hydroxamic acids.

DFT calculations carried out on zinc acetate and zinc hydroxamates using the Hartree-Fock and B3LYP methods with the 6-311+G basis set give a series of stable pseudotetrahedral chelates (ZnL(2)) (L = OAc, FA, AA, NMeAA, GA, SA). Addition of a water molecule to these chelates gives the hydrates, ZnL(2).H(2)O, which in all cases are energetically more stable than the corresponding chelate.

A novel dizinc bridged hydroxamate model for hydroxamate inhibited zinc hydrolases.

Reaction of Zn(OAc)(2).2H2O with tmen leads to the formation of [Zn(tmen)(OAc)2] (I) which reacts with benzohydroxamic acid to form Zn(BA)2.H2O (II) and the novel dizinc hydroxamate bridged complex [Zn2(mu-OAc)2(OAc)(mu-BA)(tmen)] (III), which may also be prepared by self-assembly and whose structure closely mimics that of the native hydroxamate inhibited Aeromonas proteolytica aminopeptidase.