Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

Selective gas adsorption and separation in metal–organic frameworks

Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications

From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids.

1. Introduction 20642. Synthesis of Magnetic Nanoparticles 20662.1. Classical Synthesis by Coprecipitation 20662.2. Reactions in Constrained Environments 20682.3. Hydrothermal and High-TemperatureReactions20692.4. Sol-Gel Reactions 20702.5. Polyol Methods 20712.6. Flow Injection Syntheses 20712.7. Electrochemical Methods 20712.8. Aerosol/Vapor Methods 20712.9. Sonolysis 20723. Stabilization of Magnetic Particles 20723.1. Monomeric Stabilizers 20723.1.1. Carboxylates 20733.1.2. Phosphates 20733.2. Inorganic Materials 20733.2.1. Silica 20733.2.2. Gold 20743.3. Polymer Stabilizers 20743.3.1. Dextran 20743.3.2. Polyethylene Glycol (PEG) 20753.3.3. Polyvinyl Alcohol (PVA) 20753.3.4. Alginate 20753.3.5. Chitosan 20753.3.6. Other Polymers 20753.4. Other Strategies for Stabilization 20764. Methods of Vectorization of the Particles 20765. Structural and Physicochemical Characterization 20785.1. Size, Polydispersity, Shape, and SurfaceCharacterization20795.2. Structure of Ferro- or FerrimagneticNanoparticles20805.2.1. Ferro- and Ferrimagnetic Nanoparticles 20805.3. Use of Nanoparticles as Contrast Agents forMRI20825.3.1. High Anisotropy Model 20845.3.2. Small Crystal and Low Anisotropy EnergyLimit20855.3.3. Practical Interests of Magnetic NuclearRelaxation for the Characterization ofSuperparamagnetic Colloid20855.3.4. Relaxation of Agglomerated Systems 20856. Applications 20866.1. MRI: Cellular Labeling, Molecular Imaging(Inﬂammation, Apoptose, etc.)20866.2.

Magnetic Iron Oxide Nanoparticles: Synthesis, Stabilization, Vectorization, Physicochemical Characterizations, and Biological Applications

The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

/pdf/engineering-coordination-polymers-towards-applications-3joywh2v74.pdf

Engineering coordination polymers towards applications

Magnetochemistry: advances in theory and experimentation

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.

https://science.sciencemag.org/content/sci/259/5101/1596.full.pdf

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O

The magnetic behaviour of well-dispersed monodisperse Fe3O4 nanoparticles with sizes varying between 6.6 and 17.8?nm prepared in a non-aqueous medium was investigated. The smaller nanocrystals exhibit superparamagnetism with the blocking temperatures increasing with the particle size, whereas the biggest particles are ferromagnetic at room temperature. The saturation magnetization values are slightly smaller than that of the bulk material, suggesting the existence of a disordered spin configuration on their surface. The thickness of the magnetically inert shell was estimated from the size variation of the magnetization at 1.9??. The dipole?dipole interactions between the particles were tuned by changing the interparticle distances, e.g. by diluting the nanopowders in a non-magnetic matrix at concentrations ranging from 0.25 to 100?wt%. As the strength of the interactions is decreased with dilution, the energy barrier is substantially lowered; this will induce a drastic decrease of both the blocking temperatures and the coercivity with decreasing concentration of the nanoparticles.

/pdf/magnetic-properties-of-variable-sized-fe3o4-nanoparticles-2p4w8uszr5.pdf

Magnetic Properties of Variable-sized Fe3O4 Nanoparticles Synthesized from Non-aqueous Homogeneous Solutions of Polyols

Purpose
To evaluate the effect of coating thickness on the relaxivity of iron oxide nanoparticles.

Materials and Methods
Monocrystalline superparamagnetic iron oxide nanoparticles (MIONs), coated with a polyethylene glycol (PEG)-modified, phospholipid micelle coating, with different PEG molecular weights, were prepared. The particle diameters were measured with dynamic light scattering (DLS) and electron microscopy (EM). The R1 and R2 of MIONs were measured using a bench-top nuclear magnetic resonance (NMR) relaxometer. pH was varied for some measurements. Monte Carlo simulations of proton movement in a field with nanometer-sized magnetic inhomogeneities were performed.

Results
Increasing the molecular weight of the PEG portion of the micelle coating increased overall particle diameter. As coating thickness increases, the R2 decreases and the R1 increases. Changing pH has no effect on relaxivity. The Monte Carlo simulations suggest that the effect of coating size on R2 relaxivity is determined by two competing factors: the physical exclusion of protons from the magnetic field and the residence time for protons within the coating zone.

Conclusion
Coating thickness can significantly impact the R2, and the R2/R1 ratio, of a MION contrast agent. An understanding of the relationship between coating properties and changes in relaxivity is critical for designing magnetic nanoparticle probes for molecular imaging applications using MRI. J. Magn. Reson. Imaging 2007. © 2007 Wiley-Liss, Inc.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/jmri.21194

Coating thickness of magnetic iron oxide nanoparticles affects R2 relaxivity.

(μ-Oxo)(μ-carboxylato)diiron(III) Complexes with Distinct Iron Sites. Consequences of the Inequivalence and Its Relevance to Dinuclear Iron-Oxo Proteins

Charles J. O'Connor

Papers

Magnetochemistry: advances in theory and experimentation

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O

Magnetic Properties of Variable-sized Fe3O4 Nanoparticles Synthesized from Non-aqueous Homogeneous Solutions of Polyols

Coating thickness of magnetic iron oxide nanoparticles affects R2 relaxivity.

(μ-Oxo)(μ-carboxylato)diiron(III) Complexes with Distinct Iron Sites. Consequences of the Inequivalence and Its Relevance to Dinuclear Iron-Oxo Proteins