Synthesis and Characterization of Highly Fluorinated Hydrophobic Rare-Earth Metal-Organic Frameworks (MOFs).

Tuning a material's hydrophobicity is desirable in several industrial applications, such as hydrocarbon storage, separation, selective CO capture, oil spill cleanup, and water purification. The introduction of fluorine into rare-earth (RE) metal-organic frameworks (MOFs) can make them hydrophobic. In this work, the linker bis(trifluoromethyl)terephthalic acid (TTA) was used to make highly fluorinated MOFs.

MOP-18-Derived CuO Fiber for Hybrid Supercapacitor Electrodes.

This study explores a simple method of fabricating hybrid supercapacitor electrodes, which could potentially broaden the application of this technology. The method involves electrospinning a uniform solution of Matrimid/Metal-Organic Polyhedra 18 (MOP-18) followed by carbonization at a relatively low temperature of 700 °C in air, rather than in an inert atmosphere, to create free-standing, redox-active hybrid supercapacitor electrodes. Additionally, the synthesis procedure requires no stabilization or activation steps, which enhances the cost effectiveness of the synthesized electrode materials.

Fluoro-bridged rare-earth metal-organic frameworks.

Rare-earth (RE) metal-organic frameworks (MOFs) offer unique optical, electronic, and magnetic properties. RE metals tend to make binuclear metal nodes resulting in dense nonporous coordination networks. Three dimensional porous RE-MOFs have been reported by preparing bigger metal nodes based on metal clusters often found as hexaclusters or nonaclusters.

Lanthanide Metal-Organic Frameworks Exhibiting Fluoro-Bridged Extended Chains: Synthesis, Crystal Structures, and Magnetic Properties.

Two fluoro-bridged lanthanide-containing metal-organic frameworks (MOFs) were synthesized using 2,2'-bipyridine-4,4'-dicarboxylic acid (BPDC), a fluorinated modulator, and a lanthanide nitrate. The syntheses of MOFs containing Gd or Tb and a closely related MOF structure containing Ho, Gd, or Tb are presented. The presence of the fluorinated metal chains in these MOFs is shown through single crystal X-ray diffraction, energy dispersion X-ray spectroscopy, F nuclear magnetic resonance, and X-ray photoelectron spectroscopy.

Encapsulation of ZnO and Ho:ZnO Nanoparticles in the Core of Wrinkled Mesoporous Silica.

Wrinkled mesoporous silica (WMS) has a flower- or dendritic-like morphology, tunable pore size, and highly ordered and accessible three-dimensional (3D) pore structures. In this research, a method to encapsulate semiconductor nanoparticles in the core of the wrinkled mesoporous silica during synthesis is described. Highly uniform zinc oxide and holmium-doped zinc oxide nanoparticles have been synthesized by a sonochemical method.

Pillared Carbon Membranes Derived from Cardo Polymers.

Carbon molecular sieve membranes (CMSMs) were prepared by carbonizing the high free volume polyimide BTDA-BAF that is obtained from the reaction of benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA) and 9,9-bis(4-aminophenyl) fluorene (BAF). The bulky cardo groups prevented a tight packing and rotation of the chains that leads to high permeabilities of their CMSMs. The incorporation of metal-organic polyhedra 18 (MOP-18, a copper-based MOP) in the BTDA-BAF polymer before pyrolysis at 550 °C prevented the collapse of the pores and the aging of the CMSMs.

Transformation of a copper-based metal-organic polyhedron into a mixed linker MOF for CO capture.

A new mixed linker metal-organic framework (MOF) has been synthesized from a copper-based metal-organic polyhedron (MOP-1) and 2,2'-bipyridine (2,2'-bipy). The CuMOF-Bipy with a formula of [Cu(2,2'-bpy)(-BDC)] is comprised of a binuclear Cu(II) node coordinated to 2,2'-bipy, and isophthalic acid (-BDC), which bridges to neighboring nodes. The crystal structure of CuMOF-Bipy consists of a stacked two-dimensional framework with the topology.

Synthesis of Fluoro-Bridged Ho and Gd 1,3,5-Tris(4-carboxyphenyl)benzene Metal-Organic Frameworks from Perfluoroalkyl Substances.

A new fluoro-bridged rare-earth (RE) metal-organic framework consisting of 15-connected nonanuclear and 9-connected trinuclear clusters {[RE-(μ-F)(HO)][RE(μ-F)(HO)](HCO)-(BTB)}·(solvent)x (RE = Ho and Gd) was synthesized through the transformation of a dimeric complex formulated as bis(2,2'-bipyridine)tetrakis(μ-2-fluorobenzoato-,')-bis(2-fluorobenzoato)diRE(III) with the bridging linker 1,3,5-tris(4-carboxyphenyl)benzene (HBTB). The rare-earth metal ions Ho and Gd were also found to remove fluorine from other organo-fluorine compounds such as perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA), resulting in the new fluoro-bridged RE-MOFs.

Fluorine extraction from organofluorine molecules to make fluorinated clusters in yttrium MOFs.

A new rare earth based two-dimensional coordination network and a three-dimensional metal-organic framework (MOF) have been synthesized using bicinchoninic acid (BCA) and yttrium(iii) ions. Yttrium dimer nodes are formed in the absence of a modulator, resulting in a 2D layered coordination network (Y-BCA-2D). The presence of fluorinating agents, , 2-fluorobenzoic acid (2-FBA), 2,6-difluorobenzoic acid (2,6-DFBA), and perfluorohexanoic acid (PFHxA) result in μ-F bridged metal hexaclusters (YF) that form a three-dimensional MOF (Y-BCA-3D).

Carrier gas triggered controlled biolistic delivery of DNA and protein therapeutics from metal-organic frameworks.

The efficacy and specificity of protein, DNA, and RNA-based drugs make them popular in the clinic; however, these drugs are often delivered injection, requiring skilled medical personnel, and producing biohazardous waste. Here, we report an approach that allows for their controlled delivery, affording either a burst or slow release without altering the formulation. We show that when encapsulated within zeolitic-imidazolate framework eight (ZIF-8), the biomolecules are stable in powder formulations and can be inoculated with a low-cost, gas-powered "MOF-Jet" into living animal and plant tissues.

Laminated holmium-166-containing electrospun bandages for use against skin cancer.

The number of non-melanoma skin cancer (NMSC) cases in the US will increase significantly over the next decade due to a rise in UV exposure. One of the treatment methods used to remove NMSC lesions is radiation therapy. The two types of radiation therapy used in the clinic are external beam therapy and brachytherapy.

Two-Dimensional Hexagonal-Shaped Mesoporous Carbon Sheets for Supercapacitors.

Two-dimensional mesoporous hexagonal carbon sheets (MHCSs) have been prepared via a chemical vapor deposition method employing mesoporous Mg(OH) hexagonal sheets as the template and acetylene gas as the carbon precursor. MHCSs with porosity in the micropore-mesopore range have a high specific surface area of 1785 m·g. The hierarchical microporous-mesoporous pore structure enables rapid ion transport across the hexagonal carbon sheets, resulting in superior electrochemical performance.

Graphene-like Carbon from Calcium Hydroxide.

The development of inexpensive and environmentally friendly graphene-like carbon is critical for its integration into industrial products. This work highlights the production of graphene-like carbon structures from calcium hydroxide. The chemical vapor deposition conditions to grow graphitic carbon on a calcium hydroxide catalyst are reported.

Fluoro-Bridged Clusters in Rare-Earth Metal-Organic Frameworks.

The modulator 2-fluorobenzoic acid (2-fba) is widely used to prepare RE clusters in metal-organic frameworks (MOFs). In contrast to known RE MOF structures containing hydroxide bridging groups, we report for the first time the possible presence of fluoro bridging groups in RE MOFs. In this report we discuss the synthesis of a holmium-UiO-66 analogue as well as a novel holmium MOF, where evidence of fluorinated clusters is observed.

Hybrid supercapacitors using electrodes from fibers comprising polymer blend-metal oxide composites with polymethacrylic acid as chelating agent.

Hybrid supercapacitors (SCs) made of carbon-metal oxide composites are devices which combine the advantages of electric double layer capacitors and pseudocapacitors viz high energy density, high power density and high cyclability. This is best achieved when the pseudocapacitive components are uniform in size and distribution on the conducting carbon support. Electrodes mats, fabricated from carbonized electrospun fibers generated from solutions of polyacrylonitrile (PAN) as the carbon source, cobalt (III) acetylacetonate as a metal oxide precursor, and polymethacrylic acid (PMAA) as a metal oxide precursor carrier were utilized in coin cell SCs.

The Importance of Evaluating the Lot-to-Lot Batch Consistency of Commercial Multi-Walled Carbon Nanotube Products.

The biological response of multi-walled carbon nanotubes (MWNTs) is related to their physicochemical properties and a thorough MWNT characterization should accompany an assessment of their biological activity, including their potential toxicity. Beyond characterizing the physicochemical properties of MWNTs from different sources or manufacturers, it is also important to characterize different production lots of the same MWNT product from the same vendor (i.e.

Biphenyl Wrinkled Mesoporous Silica Nanoparticles for pH-Responsive Doxorubicin Drug Delivery.

Biphenyl wrinkled mesoporous silica nanoparticles with controlled particle size and high surface area were evaluated for the storage and delivery of doxorubicin. The average particle size and surface area were ~70 nm and ~1100 m/g. The doxorubicin loading efficiency was 38.

Characterization of a Holmium 4,4'-Biphenyldicarboxylate Metal-Organic Framework and Its Potential as a Holmium Carrier System.

There is growing interest in Holmium carriers for radiotherapeutic applications. In this work, a holmium-based metal-organic framework (MOF) using the 4,4'-biphenyldicarboxylic acid (H₂BPDC) linker was synthesized and characterized to explore its potential as a radiotherapeutic carrier. The 3D MOF [Ho(BPDC)₂]·(CH₃)₂NH₂ was characterized by single crystal X-ray diffraction, FTIR, TGA and PXRD.

Binder free carbon nanofiber electrodes derived from polyacrylonitrile-lignin blends for high performance supercapacitors.

Lignin was blended with polyacrylonitrile (PAN) in different ratios and fabricated into carbon nanofiber electrodes by electrospinning followed by thermal stabilization, carbonization and subsequent activation by CO of the carbonized mats. These carbon fiber electrodes exhibit high surface area, high mesoporosity, high graphitic content and high electrical conductivity. Activated carbon nanofiber mats derived from PAN:Lignin 70:30 blends display a surface area of 2370 m g with 0.

Transition from a 1D Coordination Polymer to a Mixed-Linker Layered MOF.

A novel copper(II) metal-organic framework (MOF) has been synthesized by modifying the reaction conditions of a 1D coordination polymer. The 1D polymer is built by the coordination between copper and 2,2'-(1 H-imidazole-4,5-diyl)di-1,4,5,6-tetrahydropyrimidine (H-L1). The geometry of H-L1 precludes its ability to form extended 3D framework structures.

Selective Extraction of Thorium from Rare Earth Elements Using Wrinkled Mesoporous Carbon.

Liquid fluoride thorium reactors have been considered as replacements for uranium-based nuclear reactors, having many economic and environmental advantages. The production of thorium is usually accompanied by the separation of thorium from rare earth elements since the major thorium production mineral, monazite, contains other rare earth elements. The conventional manufacturing process involves a liquid-liquid extraction with organic ligands.

Wrinkled Mesoporous Silica Supported Lanthanum Oxide as a Template for Porous Carbon.

Wrinkled mesoporous silica (WMS) has been shown to be a promising material for catalysis and drug delivery. The WMS possesses a unique wrinkled structure with conical shaped pores radiating from the center to the surface of each particle. Lanthanum oxide was supported on wrinkled mesoporous silica as a hard template for the synthesis of graphitic carbon.

Radiotherapeutic bandage for the treatment of squamous cell carcinoma of the skin.

Introduction: Squamous cell carcinoma (SCC) is the second most common form of skin cancer in the United States. The efficacy of a pharmaceutically elegant radiotherapeutic bandage, previously described by us for application against SCC of the skin, was tested for the first time in vivo using a subcutaneous SCC mouse model and a therapeutically relevant radiation dose.

Methods: Female athymic nude mice were injected with human Colo-16 SCC cells subcutaneously and after eight days (average tumor volume: 35±8.