Magnetism of metal cyanide networks assembled at interfaces

Studies of metal cyanide thin films prepared directly at interfaces are reviewed. The systems range from monolayers, single-layer analogs of Prussian blue-like networks, to bulk powders prepared as thin films. Monolayer networks are prepared at the air/water interface and transferred to solid supports using Langmuir-Blodgett film methods. Films of bulk materials are prepared directly on solid surfaces using a templated sequential deposition procedure. The magnetic properties of the films have been explored, and in some cases, these monolayers and surface films give rise to new behavior that is only possible because of the fabrication method or thin film architecture. The methods of synthesis can generate oriented samples, even when the materials are poorly crystalline. Furthermore, the interface-assembled networks are inherently anisotropic, leading to phenomena not present in the solid-state analogs, such as anisotropic photomagnetism in a thin film of Rb_jCo_k[Fe(CN)₆]_l·nH₂O.     

Monolayers as models for supported catalysts: zirconium phosphonate films containing manganese(III) porphyrins

Organized monolayer films of a manganese tetraphenylporphyrin have been prepared and used as supported oxidation catalysts. Manganese 5,10,15,20-tetrakis(tetrafluorophenyl-4'-octadecyloxyphosphonic acid) porphyrin (1) has been immobilized as a monolayer film by a combination of Langmuir-Blodgett (LB) and self-assembled monolayer techniques that use zirconium phosphonate linkages to bind the molecule to the surface. Analysis by FTIR, XPS, UV-vis and polarized optical spectroscopy show that the films consist of noninteracting molecules effectively anchored and oriented nearly parallel to the surface. The monolayer films are stable to the solvent and temperature conditions needed to explore organic oxidations. The activity of films of 1 toward the epoxidation of cyclooctene using iodosylbenzene as the oxidant was compared to that of Manganese 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (2) and 1 under equivalent homogeneous conditions. The immobilized porphyrin 1 shows an enhanced activity relative to either homogeneous reaction. The main difference between 1 and 2 is the four alkyl phosphonate arms in 1 designed to incorporate the porphyrin within the films. The increased activity of immobilized 1 is a combination of the porphyrin structure, which prohibits the formation of mu-oxo dimers even in solution, and a change in conformation when anchored to the surface. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems.     

Metal phosphonates applied to biotechnologies: a novel approach to oligonucleotide microarrays

A new process for preparing oligonucleotide arrays is described that uses surface grafting chemistry which is fundamentally different from the electrostatic adsorption and organic covalent binding methods normally employed. Solid supports are modified with a mixed organic/inorganic zirconium phosphonate monolayer film providing a stable, well-defined interface. Oligonucleotide probes terminated with phosphate are spotted directly on to the zirconated surface forming a covalent linkage. Specific binding of terminal phosphate groups with minimal binding of the internal phosphate diesters has been demonstrated. The mixed organic/inorganic thin films have also been extended for use arraying DNA duplex probes, and therefore represent a viable general approach to DNA-based bioarrays. Ideas for interfacing mixed organic/inorganic interfaces to other bioapplications are also discussed.     

Calcium oxalate monohydrate precipitation at membrane lipid rafts

The precipitation of calcium oxalate monohydrate (COM) was monitored at a Langmuir monolayer containing lipid raft domains. The raft-forming monolayer consists of a 2:1:1 mixture of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine/sphingomyelin/dihydrocholesterol, where the raft liquid ordered phase is enriched in sphingomyelin and the sterol. COM crystals, monitored by Brewster angle microscopy, appear at the phase boundary between the raft domains and the expanded phase.     

Visual spatial memory is enhanced in female rats (but inhibited in males) by dietary soy phytoestrogens

Background  

In learning and memory tasks, requiring visual spatial memory (VSM), males exhibit superior performance to females (a difference attributed to the hormonal influence of estrogen). This study examined the influence of phytoestrogens (estrogen-like plant compounds) on VSM, utilizing radial arm-maze methods to examine varying aspects of memory. Additionally, brain phytoestrogen, calbindin (CALB), and cyclooxygenase-2 (COX-2) levels were determined.     

Towards zirconium phosphonate-based microarrays for probing DNA-protein interactions: critical influence of the location of the probe anchoring groups

Terminal phosphate groups on double-stranded DNA probes bind strongly to glass substrates coated with a zirconium phosphonate monolayer, and probes immobilized in this way as microarrays can be used to detect protein targets. The sensitivity of the microarray was shown to be enhanced by the use of a polyguanine segment ((G)n , n > or = 5) as a spacer between the phosphate linker and the protein interaction domain. More importantly, the presence of phosphate linkers on both ends of the dsDNA probes leads to significant enhancement of target capture. The relevant characteristics of the different probes when bound to the surface were determined, by the original use of a combination of surface characterization techniques (XPS, AFM, and Sarfus). In this context, the location of the phosphate linkers in the duplex probes was found to result in different probe surface coverage and presentation on the surface, which affect subsequent interactions with the target protein.     

Dimethylammonium trichlorocuprate(II): structural transition, low-temperature crystal structure, and unusual two-magnetic chain structure dictated by nonbonding chloride-chloride contacts

Catena(dimethylammonium-bis(mu2-chloro)-chlorocuprate), (CH3)2NH2CuCl3, forms chains of Cu2Cl6(2-) bifold dimers linked along the structural chain axis by terminal chlorides forming long semicoordinate bonds to adjacent dimers. The structural chains are separated by dimethylammonium ions that hydrogen bond to chloride ions of the dimers. A structural phase transition below room temperature removes disorder in the hydrogen bonding, leaving adjacent dimers along the chain structurally and magnetically inequivalent, with alternating ferromagnetic and antiferromagnetic pairs. The coupled dimers are magnetically isolated from each other along the structural chain axis by the long semicoordinate Cu-Cl bond. However, the dimers couple to like counterparts on adjacent chains via nonbonding Cl...Cl contacts. The result is two independent magnetic chains, one an alternating antiferromagnetic chain and the other an antiferromagnetic chain of ferromagnetically coupled copper dimers, which run perpendicular to the structural chains. This magnetostructural analysis is used to fit unusual low-temperature (1.6 K) magnetization vs field data that display a two-step saturation. The structural phase transition is identified with neutron scattering and capacitance measurements, and the X-ray crystal structures are determined at room temperature and 84 K. The results appear to resolve long-standing confusion about the origins of the magnetic behavior of this compound and provide a compelling example of the importance of two-halide magnetic exchange.     

Supported lipid bilayers at skeletonized surfaces for the study of transmembrane proteins

Skeletonized zirconium phosphonate surfaces are used to support planar lipid bilayers and are shown to be viable substrates for studying transmembrane proteins. The skeletonized surfaces provide space between the bilayer and the solid support to enable protein insertion and avoid denaturation. The skeletonized zirconium octadecylphosphonate surfaces were prepared using Langmuir-Blodgett techniques by mixing octadecanol with octadecylphosphonic acid. After zirconation of the transferred monolayer, rinsing the coating with organic solvent removes the octadecanol, leaving holes in the film ranging from ～50 to ～500 nm in diameter, depending on the octadecanol content. Upon subsequent deposition of a lipid bilayer, either by vesicle fusion or by Langmuir-Blodgett/Langmuir-Schaefer techniques, the lipid assemblies span the holes providing reservoirs beneath the bilayer. The viability of the supported bilayers as model membranes for transmembrane proteins was demonstrated by examining two approaches for incorporating the proteins. The BK channel protein inserts directly into a preformed bilayer on the skeletonized surface, in contrast to a bilayer on a nonskeletonized film, for which the protein associates only weakly. As a second approach, the integrin α(5)β(1) was reconstituted in lipid vesicles, and its inclusion in supported bilayers on the skeletonized surface was achieved by vesicle fusion. The integrin retains its ability to recognize the extracellular matrix protein fibronectin when supported on the skeletonized film, again in contrast to the response if the bilayer is supported on a nonskeletonized film.