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

Platonic Relationships in Metal Phosphonate Chemistry: Ionic Metal Phosphonates

Phosphonate ligands demonstrate strong affnity for metal ions. However, there are several cases where the phosphonate is found non-coordinated to the metal ion. Such compounds could be characterized as salts, since the interactions involved are ionic and hydrogen bonding. In this paper we explore a number of such examples, using divalent metal ions (Mg2+, Ca2+, Sr2+ and Ni2+) and the phosphonic acids: p-aminobenzylphosphonic acid (H2PABPA), tetramethylenediamine-tetrakis(methylenephosphonic acid) (H8TDTMP), and 1,2-ethylenediphosphonic acid (H4EDPA). The compounds isolated and structurally characterized are [Mg(H2O)6] [HPABPA]2 6H2O, [Ca(H2O)8] [HPABPA]2, [Sr(H2O)8] [HPABPA]2, [Mg(H2O)6] [H6TDTMP], and [Ni(H2O)6] [H2EDPA] H2O. Also, the coordination polymer {[Ni(4,4’-bpy)(H2O)4] [H2EDPA] H2O}n was synthesized and characterized, which contains a bridging 4,4’-bipyridine (4,4’-bpy) ligand forming an infinite chain with the Ni2+ cations. All these compounds contain the phosphonate anion as the counterion to charge balance the cationic charge originating from the metal cation.K.D.D. acknowledges the Research Committee of the University of Crete (Grant KA 10329) for financial suppor