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A novel ultramicroporous coordination polymer is prepared and is structurally characterized. The results have shown that while dehydration of the coordination polymer has negligible effect on its spin-canted antiferromagnetic behavior, C[O.sub.2] incorporation in the pores is responsible for an increment of the transition temperature at which the weak ferromagnetic ordering has taken place from 22 to 29 K.

The oxidation-induced geometrical change in [Cu-P-Cu-P] ring structures is analyzed by using quantum chemical approaches. The results have shown that the Cu-P interactions change and display partial Cu(3d) -> P donation and it is also shown that the dication has a large degree of diradical character.

A model considering various steric and stereoelectronic factors involved in transition state of the reductive elimination step is proposed and used to interpret results of systematic studies of arylcuprate conjugate addition reactions with cis and trans gamma-alkoxy-alpha,beta-enoates. While stereoselectronics disfavor syn-addition, a judicious choice of properly sized gamma-substituents might lead to the predominant formation of syn-products, especially with cis enoates.

The chemical characterization and copper binding properties of a second methanobactin, which is produced by Methylocystis strain SB2 (mb-SB2) is reported. Methanobactins is observed to make up a structurally diverse group of ribosomally produced, peptide-derived molecules, which share a common pair of five-member rings with associated enethiol groups that are able to bind, reduce and stabilize copper ions in an aqueous environment.

Heterologous expression of ATP7A or ATP7B in COS-1 cells infected with adenovirus vectors is used to characterize differential features relevant to each protein expressed in the same mammalian cell type, rather than to extrinsic factors related to different cells sustaining expression. Glycosylation of ATP7A and phosphorylation of ATP7B appears to contribute to their different trafficking and membrane association when expressed in the same cell type.

A Cu[(OTf).sub.2]-mediated Chan-Lam reaction of carboxylic acids with arylboronic acids is described, which has represented a method to access phenolic esters in good yields. The procedure has tolerated a series of functional groups like methoxycarbonyl acetoxy, free phenolic hydroxyl, vinyl, nitro, trifluoromethyl, methoxyl, bromo, chloro, iodo, and acetyl groups.

Redox and spectroscopic properties along with X-ray crystal structures are described for the type 2 [Cu.sup.II] C112D/M121E variant of Pseudomonas aeruginosa azurin. The results have highlighted the role played by outer-sphere interactions and the structural constraints they impose while determining the redox behavior of transition metal protein cofactors.

Cu-TolBINAP-catalyzed conjugate addition of Grignard reagents to 4-chloro-[alpha],[beta]-unsaturated esters, thioesters, and ketones have led to 4-chloro-3-alkyl-substituted thioesters and ketones upon protonation of the corresponding enolates at low temperatures. Tandem conjugate addition-enolate trapping has produced trans-1-alkyl-2-substituted cyclopropanes, whose versatility is shown by the formation of key intermediates for the synthesis of cascarillic acid and grenadamide.

The synthesis and characterization of a [{CuNP}.sup.10] complex is achieved by the addition of [NO][P[F.sub.6]] to copper metal powder in the presence of nitromethane. The complex has reacted with mesitylene to form [mesitylene, NO][P[F.sub.6]] and [Cu[([[eta].sup.2]-1,3,5-[Me.sub.3][C.sub.6][H.sub.3]).sub.2][P[F.sub.6]] by transfer of N[O.sup.+] to the mesitylene ring.

Q-band electron paramagnetic resonance (EPR) spectroscopy is used for showing that the polymer-chain complexes Cu[(hfac).sub.2][L.sup.R] are one-dimensional in the sense of the topology of their exchange channels, but the magnetic chains spread across the structural polymer chains and consist solely of spin triads of nitroxide-copper(II)-nitroxide. The studies have provided insights into the cooperativity effects and mechanisms of magnetic anomalies in the Cu[(hfac).sub.2][L.sup.R] family of molecular magnets.

The regulatory effect of copper binding to the copper-domain domains of ATP7B is understood by performing NMR characterization of WCBD (the N-terminus of ATP7B comprised of six copper-binding domains 4-6). The copper transfer to and between the N-terminal domains of the Wilson Cu-ATPase has occurred through protein interactions that are facilitated by the flexibility of the linkers and the motional freedom of the domains with respect to each other.

A pent-4-ynyl tert-butyl N,N-diisopropyl phosphoramidite is coupled at the 5' -end of oligonucleotides to produce a phosphite triester linkage, which has formed an H-phosphonate diester linkage during treatment with dichloroacetic acid. An amidative oxidation with C[Cl.sub.4] in the presence of an amine and a 1,3-dipolar cycloaddition with an azide under copper(I) catalysis has produced the bis-conjugated oligonucleotides with high efficiency.

The effect of auxiliary ligands near the azido group other than pyridyl for [Cu.sup.II] on the efficiency of the Cu[(OAc).sub.2]-accelerated azide-alkyne cycloaddition (AAC) reaction is examined. The structure of [Cu([bidentate.sub.2])[([H.sub.2]O).sub.2]][(Cl[O.sub.4]).sub.2] has shown the synergistic effect of hydrogen bonding, [pi]-[pi] stacking interactions, and metal coordination in forming a one-dimensional supramolecular construct in the solid state.

Base-functionalized aza-bis(oxazoline) ligands are prepared to analyze the concept of dual activation through the Lewis acid and a tethered amine base and the catalytic activity of the Cu complex is studied for the asymmetric Henry reaction. The ethylpiperazine-functionalized aza-bis(oxazoline) copper catalyst has resulted in rate acceleration and also improved enantioselectivity.

The kinetics, thermodynamics and coordination dynamics for [O.sub.2] and CO 1:1 binding to a series of pseudo-tetradentate ligand-copper(I) complexes ([super D]L[Cu.sup.I]) to give [[Cu.sup.I]/[O.sub.2] and [Cu.sup.I]/CO product species are reported. The results demonstrated that subtle changes in the coordination environment which occur over period of time through evolution in nature or through controlled ligand design in synthetic systems critically influence the detailed level of the observed chemistry in terms of reaction kinetics, structure and reactivity and hence the function.

Electrospray-mass spectrometry (ES?MS) was employed to confirm the formation of the [Cu.sup.2+] complex with [alpha]-syn or with an N-terminal peptide, [alpha]-synuclein which play an important role in neuropathology in ParkinsonEs disease (PD). The results provide insight into partial role of oxidative stress for the loss of dopaminergic cells in PD brain and the multifaceted role of the [alpha]-syn-[Cu.sup.2+] complex in oxidative stress associated with PD symptoms.

Chiral amino alcohols supported on mesoporous silicas are prepared and studied as a new class of chiral ligands in copper-catalyzed nitroaldol reaction under heterogeneous and mild reaction conditions. The heterogenized chiral copper(II) complex of amino alcohol is an effective recyclable catalyst for the nitroaldol reaction of different aldehydes like aromatic, aliphatic, alicyclic and [alpha]-[beta] unsaturated aldehydes to produce nitroaldol products with very high enantioselectivity.

A study was conducted to explore the reaction of the doubly oxidized [beta]-octaisobutyl-meso-tetraphenylporphyrin (OiBTPP), which has a 16 [pi]-electronic structure at the porphyrin core, with a variety of metal reagents. Electrochemical and thin-layer UV-vis spectroelectrochemical experiments on OiBTPP (16[pi]) and [(OiBTPP)Zn(Cl)]+[Zn[Cl.sup.3]](-) (16[pi]) indicated that both compounds could be electroreduced to give the 18[pi] species, with the 16[pi]/18[pi] transition which is reversible in the case of [(OiBTPP)Zn(Cl)]+[Zn[Cl.sup.3]](-).

A study was conducted to understand the mechanism underlying copper homeostasis in copper site structures such as metallochaperone Atx1. The results offer insight into the copper-induced switch in Atx1 dimer structure which might have a regulatory role with cluster formation helping to buffer copper.

Mechanistic details of a mild aromatic C-H activation effected by a copper(II) center ligated in a triazamacrocylic ligand which produce equimolar amounts of a [Cu.sup.III]-aryl species and [Cu.sup.I] species as reaction products is reported. The reaction kinetics strongly implicates a rate-limiting proton-coupled electron transfer as the key C-H activation step and the mechanism does not conform to the C-H activation mechanism in a [Ni.sup.II] analogue.

An alkaline microfluidic [H.sub.2]/[O.sub.2] fuel cell is used to study the performance of a novel carbon-supported copper complex of 3,5-diamino-1,2,4-triazole (Cu-tri/C) as a cathode material. The absolute Cu-tri/C cathode performance is comparable to that of a Pt/C cathode and the and the performance and durability might be realized by optimizing catalyst and electrode preparation procedures.