Divalent metal phosphonate coordination polymers constructed from a dipiperidine-based bisphosphonate ligand

The ligand 4,4'-dipiperidine-N,N'-bis(methylenephosphonic acid), H(4)L, has been reacted with divalent metal salts under solvothermal conditions to yield seven new metal phosphonate coordination polymers. The compounds have been characterized by elemental analyses and their structures determined by single-crystal X-ray diffraction. Zn(2)(L)(H(2)O)(2) and Co(2)(L)(H(2)O)(2) have (different) layered structures, while Mn(2)(L)(H(2)O)(3) has a chain motif. In these compounds, the N atoms of the ligand bind to the metal ions. α-Co(2)Cl(2)(H(2)L), formed from CoCl(2)·6H(2)O and H(4)L in ethanol, is also layered but the N atoms of the ligand are protonated. The Co atoms are tetrahedral, coordinated by three phosphonate oxygen atoms and a chloride ion. A polymorph of this compound, β-Co(2)Cl(2)(H(2)L), was obtained from a mixed ionic liquid under microwave irradiation. The primary difference between the polymorphs is the orientation of the phosphonate group relative to the dipiperidine. When reacted hydrothermally with Sn(II)C(2)O(4), H(4)L partially decomposes, producing phosphate ions which are incorporated into the structure of Sn(6)O(2)(H(2)L)(PO(4))(2)·4H(2)O. In this compound, the N atoms of the ligand are protonated, and two oxide anions are incorporated for charge balance. A second phase is obtained from the same reaction, which was determined to be Sn(7)O(L)(3). This compound has a layered structure which contains relatively large voids within the inorganic portion of the layer. These structures are discussed, as well as factors influencing the state of protonation in the final compounds. The choice of solvent and temperature were found to have a significant influence on the type of structure obtained.     

Membraneless, room-temperature, direct borohydride/cerium fuel cell with power density of over 0.25 W/cm2

The widespread adoption and deployment of fuel cells as an alternative energy technology have been hampered by a number of formidable technical challenges, including the cost and long-term stability of electrocatalyst and membrane materials. We present a microfluidic fuel cell that overcomes many of these obstacles while achieving power densities in excess of 250 mW/cm(2). The poisoning and sluggish reaction rate associated with CO-contaminated H(2) and methanol, respectively, are averted by employing the promising, high-energy density fuel borohydride. The high-overpotential reaction of oxygen gas at the cathode is supplanted by the high-voltage reduction of cerium ammonium nitrate. Expensive, ineffective membrane materials are replaced with laminar flow and a nonselective, porous convection barrier to separate the fuel and oxidant streams. The result is a Nafion-free, room-temperature fuel cell that has the highest power density per unit mass of Pt catalyst employed for a non-H(2) fuel cell, and exceeds the power density of a typical H(2) fuel cell by 50%.     

Structure of mercaptobiphenyl monolayers on mercury

The molecular-scale structure and phase behavior of single-component Langmuir films of 4'-methyl-4-mercaptobiphenyl (MMB) and 4'-perfluoromethyl-4-mercaptobiphenyl (FMMB) on mercury were studied using surface tensiometry, grazing incidence X-ray diffraction, and X-ray reflectivity. At low coverages, a condensed but in-plane disordered single layer of surface-parallel molecules is found for both compounds. At high coverages, both compounds exhibit in-plane-ordered phases of standing-up molecules. For MMB, the biphenyl core dominates the structure, yielding a centered-rectangular unit cell with an area A(x) of 21.8 A(2)/molecule, with molecules tilted by approximately 14 degrees from the surface normal in the nearest-neighbor direction, and a coherence length xi of >1000 A for the crystalline domains. For FMMB, the perfluoromethyl group dominates the structure, yielding a hexagonal unit cell with untilted molecules, an area A(x) of 24.2 A(2)/molecule, and a much smaller xi of approximately 110 A. The structure is discussed in comparison with self-assembled monolayers of MMB on crystalline Au(111) and similar-length alkanethiolate SAMs on Au(111) and on mercury. The differences in the structure are discussed and traced to the differences in the substrate's surface structure, and in the molecular cross section and rigidity.     

Correlation of the Solubilizing Abilities of 1-Butyl-1-methyl-pyrrolidinium Tris(pentafluoroethyl)trifluorophosphate, 1-Butyl-1-methylpyrrolidinium Triflate and 1-Methoxyethyl-1-methylmorpholinium Tris(pentafluoroethyl)trifluorophosphate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrolidinium tris(pentafluoroethyl)trifluorophosphate ([BMPyrr]⁺[FAP]^?), 1-butyl-1-methylpyrrolidinium triflate, ([BMPyrr]⁺[Trif]^?), and 1-methoxyethyl-1-methylmorpholinium tris(pentafluoroethyl)trifluorophosphate, ([MeoeMMorp]⁺[FAP]^?), stationary phases at (323, 353 and 383) K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) and water-to-anhydrous IL partition coefficients. The three sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.11 and 0.15 log₁₀ units, respectively.     

Surface morphological and impedance spectroscopic studies on the interaction of polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP) with mild steel in acid solutions

The inhibition of mild steel corrosion in aerated acid mixture of 0.5 N H₂SO₄ and 0.5 N HCl solution was investigated using potentiodynamic polarization studies, linear polarization studies, electrochemical impedance spectroscopy, adsorption, and surface morphological studies. The effect of inhibitor concentration on corrosion rate, degree of surface coverage, adsorption kinetics, and surface morphology is investigated. The inhibition efficiency increased markedly with increase in additive concentration. The presence of PEG and PVP decreases the double-layer capacitance and increases the charge-transfer resistance. The inhibitor molecules first adsorb on the metal surface following a Langmuir adsorption isotherm. Both PEG and PVP offer good inhibition properties for mild steel and act as mixed-type inhibitors. Surface analysis by scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows that PVP offers better protection than PEG.     

Integrated Ion Exchange and Liquid-Liquid Extraction Process for the Separation of Platinum Group Metals (PGM)

A process for concentration and separation of platinum group metals (PGM) by a combination of ion exchange and liquid-liquid extraction is presented. First the PGM metals are dissolved by HC1/C1₁ and then passed through an isothiouronium anion exchange resin, where specific absorption occurs. The thiourea eluate from the resin is converted to the chloride complexes. Further hydrolysis (conditioning) yields an aqueous feed to a liquid-liquid extraction step, with Alamine-336. Platinum and palladium are very well extracted, while most of the other PGM are rejected in the aqueous phase. The liquid-liquid extraction can be used by itself, if the level of the base metals does not exceed the concentration of the PGM ions.

Platinum and palladium are now separated from each other by the selective stripping of palladium with thiourea, and platinum with thiocyanate.

The paper discusses the extraction chemistry of all the steps, and provides also experimental pilot-plant results.     

Protein-Polysaccharide Interactions for Stabilization of Food Emulsions

Proteins, polysaccharides and their blends, as examples of natural biopolymers, are surface active materials. Biopolymers may be considered as amphiphilic macromolecules that play an essential role in stabilizing food formulations (foams, emulsions and dispersions). Under specific conditions (such as protein-to-polysaccharide ratio, pH, ionic strength, temperature, mixing processing), it has been stated that proteins and polysaccharides form hybrids (complexes) with enhanced functional properties in comparison to the proteins and polysaccharides alone. Different protein-polysaccharide pairs are reviewed with particular attention to the emulsification capability of their mixtures. In the case of uncomplexed blends of biopolymers, competitive adsorption onto hydrophobic surfaces is generally reported. Conversely, electrostatic complexation between oppositely charged proteins and polysaccharides allows better anchoring of the new-formed macro-molecular amphiphile onto oil-water interfaces. Moreover, improved thermal stability and increased resistance to external treatment (high pressure) involved in food processing are obtained. This review presents basic and applied knowledge on protein-polysaccharide interactions in aqueous medium and at the oil-water interface in food emulsion systems. Electrostatic interactions and thermodynamic incompatibility in mixed biopolymer solutions are correlated to the functional properties (rheology, surface hydrophobiciry, emulsification power) of these interesting blends. Basic and industrial selected systems of different families of hydrocolloids (as gum Arabic, galactomannans, pectins) and protein (caseins, whey, soya, gelatin) mixtures are reviewed.     

SOME REACTIONS OF ALIPHATIC AMIDES WITH SULFUR AND SODIUM POLYSULFIDES

Abstract

Some reactions of the aliphatic amides, CH₃CONH₂, CH₃CONHCH₃, CH₃CON(CH₃)₂ and CH₃CON(C₂H₅)₂ with elemental S and sodium sulfides, Na₂S _n , n ≥ 1, have been studied. The initial reaction product with elemental sulfur appears to be a substituted polysulfane, CH₃COS _n NR, formed by the insertion of the sulfur chain into the C[sbnd]N bond. This product decomposes on further heating, forming COS as the major gas product. In solutions of Na₂S _n in the amides, the reactive material appears to be elemental S, present in equilibrium with S _n ^?2. In the N-dialkyl substituted amides, CH₃CON(CH₃)₂ and CH₃CON(C₂H₅)₂, the tetrasulfide is uniquely stabilized by solvent coordination so that solutions of Na₂S₄ in these amides are stable for long periods of time at 130°C.     

Synthesis and evaluation of iron chelators with masked hydrophilic moieties

Synthetic iron chelators based on the natural siderophore ferrichrome have previously been shown to bind Fe(III) with high affinity (pKf > 27) and have shown no toxicity to mammalian cell cultures in vitro. A new class of lipophilic ferrichrome analogues carrying acetoxymethyl ester moieties has been synthesized. We have shown that these molecules penetrate rapidly through cell membranes and turn highly hydrophilic while inside the cells, upon esterase mediated hydrolysis of the lipophilic termini. The intracellular retention was visualized by labeling these analogues with a fluorescent naphthalic diimide probe. The prohydrophilic iron chelators have been shown to inhibit the metal-catalyzed intracellular formation of reactive oxygen species with high effectivity, and preliminary results suggest these molecules to be potent antimalarial agents.