Tailored novel phosphonate-based hybrid materials by design for diverse applications

Hybrid materials are composed of an organic and an inorganic part, placed together in such a way that the final product has defined structures and properties. Among the plethora of hybrid materials, coordination polymers combine an organic linker and a metal site, thus creating 1D, 2D, and 3D architectures. A class of coordination polymers based on metal phosphonates utilize (poly)phosphonic acids as linkers. In this presentation, the following concepts will be discussed: (a) Synthetic efforts and factors that influence reaction paths (b) Physicochemical characterization (c) Structural chemistry (d) Framework interconversions (e) Applications in proton conductivity (f) Applications in pharmaceutical sciences (g) Applications in archaeology and cultural heritageUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. MINECO: MAT2016-77648-

Inorganic materials in industrial processes

Although inorganic materials represent a small number to the extreme number of the organic ones, they play a number of crucial roles in several processes of industrial interest. Two significant technologically processes have been selected as “case studies” for this presentation: metallic corrosion and its control, and mitigation of inorganic deposits, both related to industrial water systems.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Drug Delivery Systems based on hydrogels

Gel systems have found extensive applications in the medicinal/pharmaceutical field because of their ease of preparation, ability for modifications, and responsiveness to external chemical or physical stimuli. Gels usually act as hosts for active pharmaceutical agents for a variety of pathological conditions. They function as controllers of the release of pharmaceuticals that have proven to be “problematic” because they are either unsuitably insoluble to biological fluids, or they are metabolized unacceptably rapidly. In this presentation the use of silica-based hydrogels as controlled release drug delivery systems will be discussed, with emphasis on drugs against osteoporosisUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Metal Phosphonate MOFs: Attractive properties for exploitation

The field of phosphonate-based MOFs has known a significant renaissance during the last decade. Apart from academic curiosity, such materials are sought for their superior properties, stability (towards high Ts and hydrolysis) and functionality. Their amazing structural variability notwithstanding, these properties make them suitable candidates for a variety of applications. In this presentation a variety of such attractive properties will be shown that are geared towards specific potential applications. These include gas absorption, proton conductivity, corrosion control, photoluminescence, metal ion absorption, etc.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Gels: formation, structure and utilization in crystal growth

Gels are ubiquitous in Nature and everyday life. This presentation will focus on the utilization of gels in the art of crystal growing. Several scientific disciplines depend on formation and characterization of crystals. Numerous times to obtain a single crystal is necessary for full identification of a new compound or a pharmaceutical ingredient. Specific cases will be presented on the successful use of gel systems in crystal growth.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Chemistry of Organophosphonate Scale Growth lnhibitors: 3. Physicochemical Aspects of 2-Phosphonobutane-1,2,4-Tricarboxylate (PBTC) And Its Effect on CaCO3 Crystal Growth

Industrial water systems often suffer from undesirable inorganic deposits, such as calcium carbonate, calcium phosphates, calcium sulfate, magnesium silicate, and others. Synthetic water additives, such as phosphonates and phosphonocarboxylates, are the most important and widely utilized scale inhibitors in a plethora of industrial applications including cooling water, geothermal drilling, desalination, etc. The design of efficient and cost-effective inhibitors, as well as the study of their structure and function at the molecular level are important areas of research. This study reports various physicochemical aspects of the chemistry of PBTC (PBTC = 2-phosphonobutane-1,2,4-tricarboxylic acid), one of the most widely used scale inhibitors in the cooling water treatment industry. These aspects include its CaCO3 crystal growth inhibition and modification properties under severe conditions of high CaCO3 supersaturation, stability towards oxidizing microbiocides and tolerance towards precipitation with Ca2+. Results show that 15 ppm of PBTC can inhibit the formation of by ∼35 %, 30 ppm by ∼40 %, and 60 ppm by ∼44 %. PBTC is virtually stable to the effects of a variety of oxidizing microbiocides, including chlorine, bromine and others. PBTC shows excellent tolerance towards precipitation as its Ca salt. Precipitation in a 1000 ppm Ca2+ (as CaCO3) occurs after 185 ppm PBTC are present

Chemistry of Organophosphonate Scale Growth lnhibitors: 2. Structural Aspects of 2-Phosphonobutane-1,2,4-Tricarboxylic Acid Monohydrate (PBTC.H2O)

Industrial water systems often suffer from undesirable inorganic deposits, such as calcium carbonate, calcium phosphate(s), magnesium silicate, and others. Synthetic water additives such as phosphonates and phosphonocarboxylates are the most important and widely utilized scale inhibitors in a plethora of industrial applications. The design of efficient and cost-effective inhibitors, as well as the study of their structure and function at the molecular level are important areas of research. This study reports the crystal and molecular structure of PBTC (PBTC = 2-phosphonobutane-1,2,4-tricarboxylic acid), one of the most widely used scale inhibitors in the cooling water treatment industry. Triclinic PBTC monohydrate crystallizes in the P 1 space group with cell dimesions, a =7.671(1) Å, b = 8.680(1) Å, c = 9.886(1) Å, α = 65.518(2) deg, β = 71.683(2) deg, γ = 76.173(2) deg, V = 564.20(11) Å3, and Z = 2. Bond distances in the -PO3 moiety are 1.4928(10) Å for the P=O double bond and 1.5294(10) Å and 1.5578(10) Å for the two -P-O(H) groups. P-C and C-O bond lengths fall in the normal range. A network of hydrogen bonds are formed between the water molecule of crystallization, the -P-OH and the -COOH groups

New multifunctional sulfonato-containing metal phosphonates proton conductors

Anchoring of acidic functional groups to organic linkers acting as ligands in metal phosphonates has been demonstrate to be a valid strategy to develop new proton conductor materials, which exhibit tunable properties and are potentially applicable to proton exchange membranes, such as those used in PEMFCs [1,2]. In this work, the structural and proton conductivity properties of several families of divalent and trivalent metal amino-sulfophosphonates are presented. The chosen ligand, (H2O3PCH2)2-N-(CH2)2-SO3H, was reacted with the appropriate metal salt using highthrough-put screening and/or microwave-assisted synthesis. Different crystal structures haven been solved displaying a variety of metal ligand coordination modes, in whose frameworks acidic groups contribute to create strong H-bond networks; together with lattice and bound water molecules. Proton conductivity values oscillate between 10-4 and 10-2 S.cm-1, at 80 ºC and 95 % relative humidity, most of them showing activation energies characteristic of a Grotthuss-type proton transport mechanism.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. MINECO: MAT2016-77648-R Junta de Andalucía: P-12-FQM-1656 y FQM-11

Proton conductivity and luminiscence properties of lanthanide aminotriphosphonates

Metal phosphonates are multifunctional solids with tunable properties, such as internal H-bond networks, and high chemical and thermal stability [1]. In the present work, we describe the synthesis, structural characterization, luminescent properties and proton conduction performance of a new family of isostructural cationic compounds with general formula [Ln(H4NMP)(H2O)2]Cl·2H2O [Ln = La3+, Pr3+, Sm3+, Gd3+, Tb3+, Dy3+, Ho3+, H6NMP = nitrilotris(methylphosphonic acid)]. These solids are formed by positively charge layers, which consist of isolated LnO8 polyhedra and bridge chelating NMP2- ligands, held apart by chloride ions and water molecules. This arrangement result in extended interlayer hydrogen networks with possible proton transfer pathways. The proton conductivity of Gd3+ sample, selected as prototype of the series, was measured. In the range between range 25º and 80 ºC, the conductivity increase with the temperature up to a maximum value of 3.10-4 S·cm-1, at relative humidity of 95 %. The activation energy obtained from the Arrhenius plot (Figure 1) is in the range corresponding to a Grotthuss transfer mechanism.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. FQM-1656; MAT2013-41836-R