Diffusion of ferrocene through vanadyl phosphate by density functional theory.

Here, we employed the nudged elastic band (NEB) method to simulate the diffusion of ferrocene through vanadyl phosphate (VOPO), with a focus on understanding the diffusion pathways arising from the complex structure of ferrocene. We systematically evaluated a total of 36 potential diffusion paths, categorizing them into three groups based on their directional orientation: 15 paths between V sites along the [110] direction, 15 paths from V to P sites along the [100] direction, and 6 paths between P sites also along the [110] direction. Our analysis revealed that the energy barriers for diffusion along the [110] direction typically ranged between 0.

Chelation-assisted assembly of multidentate colloidal nanoparticles into metal-organic nanoparticles.

We propose a chelation-assisted assembly of multidentate CNs into metal-organic nanoparticles (MONs). Multidentate CNs functionalized with coordination sites participate equally as organic linkers in MON construction, which is driven by chelation between metal ions and coordination sites. MONs assembled from Au nanoparticles display particle number- and size-dependent optical properties.

Control of the Speed of a Light-Induced Spin Transition through Mesoscale Core-Shell Architecture.

The rate of the light-induced spin transition in a coordination polymer network solid dramatically increases when included as the core in mesoscale core-shell particles. A series of photomagnetic coordination polymer core-shell heterostructures, based on the light-switchable Rb Co [Fe(CN)] · mHO (RbCoFe-PBA) as core with the isostructural K Ni [Cr(CN)] · nHO (KNiCr-PBA) as shell, are studied using temperature-dependent powder X-ray diffraction and SQUID magnetometry. The core RbCoFe-PBA exhibits a charge transfer-induced spin transition (CTIST), which can be thermally and optically induced.

Synergistic photomagnetic effects in coordination polymer heterostructure particles of Hofmann-like Fe(4-phenylpyridine)[Ni(CN)]·0.5HO and KNi[Cr(CN)]·nHO.

New nanometer scale heterostructure particles of the two-dimensional Hofmann-like Fe(ii) spin-crossover network, Fe(phpy)[Ni(CN)]·0.5HO {phpy = 4-phenylpyridine}, and the Prussian blue analogue KNi[Cr(CN)]·nHO (NiCr-PBA) have been developed, exhibiting synergistic photomagnetic effects, whereby the LIESST (light-induced electron spin-state trapping) effect in the Hofmann-like material induces a magnetization change in the NiCr-PBA. A variety of microscopic and spectroscopic techniques demonstrate the heterogeneous growth of the NiCr-PBA on the Hofmann seed particles and show the Hofmann compound retains its thermal and photoinduced spin transition properties in the heterostructure.

Assembly of Double-Hydrophilic Block Copolymers Triggered by Gadolinium Ions: New Colloidal MRI Contrast Agents.

Mixing double-hydrophilic block copolymers containing a poly(acrylic acid) block with gadolinium ions in water leads to the spontaneous formation of polymeric nanoparticles. With an average diameter near 20 nm, the nanoparticles are exceptionally stable, even after dilution and over a large range of pH and ionic strength. High magnetic relaxivities were measured in vitro for these biocompatible colloids, and in vivo magnetic resonance imaging on rats demonstrates the potential utility of such polymeric assemblies.

Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins.

Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate.

Antiferromagnetic ordering in MnF(salen).

Antiferromagnetic order at [Formula: see text] K has been identified in Mn(III)F(salen), salen  =  H14C16N2O2, an S  =  2 linear-chain system. Using single crystals, specific heat studies performed in magnetic fields up to 9 T revealed the presence of a field-independent cusp at the same temperature where (1)H NMR studies conducted at 42 MHz observed dramatic changes in the spin-lattice relaxation time, T 1, and in the linewidths. Low-field (less than 0.

Hyperbranched polymer mediated size-controlled synthesis of gadolinium phosphate nanoparticles: colloidal properties and particle size-dependence on MRI relaxivity.

Hyperbranched polymers based on the poly(amidoamine), HyPAM, were used to synthesize gadolinium phosphate nanowires under mild conditions. Control of the average particle size was obtained by adjusting polymer concentration. Proton relaxivity measurements reveal an optimum particle size, reaching relaxivity values as high as 55 ± 9 mM(-1) s(-1) for r1 and 67 ± 11 mM(-1) s(-1) for r2.

Direct Observation of Short-Range Structural Coherence During a Charge Transfer Induced Spin Transition in a CoFe Prussian Blue Analogue by Transmission Electron Microscopy.

The local structure within the Co-Fe atomic array of the photoswitchable coordination polymer magnet, K0.3Co[Fe(CN)6]0.77·nH2O, is directly observed during charge transfer induced spin transition (CTIST), a solid-solid phase change, using high-resolution transmission electron microscopy (HRTEM).

One-step synthesis of gradient gadolinium ironhexacyanoferrate nanoparticles: a new particle design easily combining MRI contrast and photothermal therapy.

A one-step synthesis of Prussian blue nanoparticles possessing a concentration gradient of Gd3+ counterions, g-Gd-PB, has been developed, and the potential for the particles to perform as both MRI positive contrast agents and photothermal therapy agents is demonstrated. The synthesis of potassium/gadolinium ironhexacyanoferrate is performed under increasing concentration of Gd3+ ions forming particles with a higher concentration of gadolinium toward the outer layers. The proton relaxivity (r1) measured for the particles is 12.

Design and optimization of a phosphopeptide anchor for specific immobilization of a capture protein on zirconium phosphonate modified supports.

The attachment of affinity proteins onto zirconium phosphonate coated glass slides was investigated by fusing a short phosphorylated peptide sequence at one extremity to enable selective bonding to the active surface via the formation of zirconium phosphate coordinate covalent bonds. In a model study, the binding of short peptides containing zero to four phosphorylated serine units and a biotin end-group was assessed by surface plasmon resonance-enhanced ellipsometry (SPREE) as well as in a microarray format using fluorescence detection of AlexaFluor 647-labeled streptavidin. Significant binding to the zirconated surface was only observed in the case of the phosphopeptides, with the best performance, as judged by streptavidin capture, observed for peptides with three or four phosphorylation sites and when spotted at pH 3.

Light-induced changes in magnetism in a coordination polymer heterostructure, Rb0.24Co[Fe(CN)6]0.74@K0.10Co[Cr(CN)6]0.70·nH2O and the role of the shell thickness on the properties of both core and shell.

Particles of formula Rb0.24Co[Fe(CN)6]0.74@K0.

Light-induced magnetization changes in a coordination polymer heterostructure of a Prussian blue analogue and a Hofmann-like Fe(II) spin crossover compound.

Coordination polymer thin film heterostructures of the Prussian blue analogue Ni(II)b[Cr(III)(CN)6](0.7)·nH2O (NiCr-PBA) and the 3D Hofmann-like spin crossover compound Fe(azpy)[Pt(CN)4]·xH2O {azpy = 4,4'-azopyridine} have been developed, and spin transition properties have been characterized via SQUID magnetometry and Raman spectroscopy. The magnetic response of the ferromagnetic NiCr-PBA layer (T(c) ≈ 70 K) can be altered by inducing the LIESST effect (light-induced excited spin state trapping) in the coupled paramagnetic Fe(II) spin crossover material.

Size-dependent MRI relaxivity and dual imaging with Eu0.2Gd0.8PO4·H2O nanoparticles.

Three different sizes of Eu0.2Gd0.8PO4·H2O nanoparticles have been prepared to investigate the particle size influence on water proton relaxivity.

High rate sodium ion insertion into core-shell nanoparticles of Prussian blue analogues.

We demonstrate that core-shell nanoparticles consisting of two different Prussian blue analogues, one high capacity and the other robust, can provide enhanced rate capability as cathode materials in sodium-ion batteries.

Synthesis and size control of iron(II) hexacyanochromate(III) nanoparticles and the effect of particle size on linkage isomerism.

The controlled synthesis of monodisperse nanoparticles of the cubic Prussian blue analogue iron(II) hexacyanochromate(III) is reported along with a kinetic study, using cyanide stretching frequencies, showing the variations of the activation energy (E(a)) of the linkage isomerism as a function of the particle size. Highly reproducible, cubic-shaped iron(II) hexacyanochromate(III) nanocrystals, with sizes ranging from 2 to 50 nm, are synthesized using a microemulsion technique, whereas a bulk synthesis yields nonuniform less monodisperse particles with sizes greater than 100 nm. Monitoring the cyanide stretching frequency with FTIR spectroscopy shows that the rate of isomerization is faster for smaller particles.

Bimetallic cyanide-bridged coordination polymers as lithium ion cathode materials: core@shell nanoparticles with enhanced cyclability.

Prussian blue analogues (PBAs) have recently been proposed as electrode materials for low-cost, long-cycle-life, and high-power batteries. However, high-capacity bimetallic examples show poor cycle stability due to surface instabilities of the reduced states. The present work demonstrates that, relative to single-component materials, higher capacity and longer cycle stability are achieved when using Prussian blue analogue core@shell particle heterostructures as the cathode material for Li-ion storage.

DNA surface modified gadolinium phosphate nanoparticles as MRI contrast agents.

Oligonucleotide modified gadolinium phosphate nanoparticles have been prepared and their magnetic resonance relaxivity properties measured. Nanoparticles of GdPO4·H2O were synthesized in a water/oil microemulsion using IGEPAL CO-520 as surfactant, resulting in 50 to 100 nm particles that are highly dispersible and stable in water. Using surface modification chemistry previously established for zirconium phosphonate surfaces, the particles are directly modified with 5'-phosphate terminated oligonucleotides, and the specific interaction of the divalent phosphate with Gd(3+) sites at the surface is demonstrated.

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.

Engineering of a phosphorylatable tag for specific protein binding on zirconium phosphonate based microarrays.

A phosphorylatable tag was designed and fused at the C-terminal end of proteins, which allowed efficient and oriented immobilization of capture proteins on glass substrates coated with a zirconium phosphonate monolayer. The concept is demonstrated using Nanofitin directed against lysozyme. This peptide tag (DSDSSSEDE) contains four serines in an acidic environment, which favored its in vitro phosphorylation by casein kinase II.

Photoinduced magnetism in core/shell Prussian blue analogue heterostructures of K(j)Ni(k)[Cr(CN)6]l·nH2O with Rb(a)Co(b)[Fe(CN)6]c·mH2O.

Core/shell and core/shell/shell particles comprised of the Prussian blue analogues K(j)Ni(k)[Cr(CN)(6)](l)·nH(2)O (A) and Rb(a)Co(b)[Fe(CN)(6)](c)·mH(2)O (B) have been prepared for the purpose of studying persistent photoinduced magnetization in the heterostructures. Synthetic procedures have been refined to allow controlled growth of relatively thick (50-100 nm) consecutive layers of the Prussian blue analogues while minimizing the mixing of materials at the interfaces. Through changes in the order in which the two components are added, particles with AB, ABA, BA, and BAB sequences have been prepared.

Thin films of coordination polymer magnets.

Many applications of molecule based magnets, whether they are in information storage, displays, or as components in electronic or spintronic devices, will require putting the active materials on a surface or interfacing them with other components. Although there are many examples of molecule-based magnets, the families of tetracyanoethylene (TCNE) based magnets and Prussian-blue analogs possess materials properties that are close to those required for practical applications, and are the most advanced with respect to studies as thin films. This critical review focuses on fabrication and characterization of thin films of TCNE and Prussian-blue analog coordination polymer magnets.

Persistent photoinduced magnetism in heterostructures of prussian blue analogues.

Heterostructured ABA thin films consisting of two different Prussian blue analogues, where A is a ferromagnet and B is a photoinducible ferrimagnet, have been fabricated for the first time. This novel arrangement allows the magnetization to be decreased by irradiation with white light and significantly increases the ordering temperature of the photoinduced magnetism from 18 to 75 K.

Effect of phospholipase A2 hydrolysis products on calcium oxalate precipitation at lipid interfaces.

Urinary stones are commonly composed of an inorganic component, calcium oxalate, or calcium phosphate and an organic matrix of lipids, carbohydrates, and proteinaceous matter. Of interest is the role that the organic matrix elements may play as catalysts for the heterogeneous nucleation of the calcium salts, and a number of studies have examined the role of lipids in calcium oxalate monohydrate (COM) formation. In this study, products of lipid hydrolysis from phospholipase A(2) (PLA(2)) are examined for their effect on COM formation using Langmuir monolayers as model lipid membrane assemblies.

Bisphosphonate adaptors for specific protein binding on zirconium phosphonate-based microarrays.

Two bisphosphonate adaptors were designed to immobilize histidine-tagged proteins onto glass substrates coated with a zirconium phosphonate monolayer, allowing efficient and oriented immobilization of capture proteins, affitins directed to lysozyme, on a microarray format. These bifunctional adaptors contain two phosphonic acid anchors at one extremity and either one nitrilotriacetic acid (NTA) or two NTA groups at the other. The phosphonate groups provide a stable bond to the zirconium interface by multipoint attachment and allow high density of surface coverage of the linkers as revealed by X-ray photoelectron spectroscopy (XPS).