Single-phase gold/palladium catalyst: The nature of synergistic effect

The liquid phase oxidation of glycerol with oxygen has been studied using mono and bimetallic catalysts based on Au and Pd metals supported on activated carbon, in order to study the effect of the metal on the distribution of the products and on activity of catalysts. It was found that by using bimetallic catalysts (Au–Pd) a strong synergistic effect was shown. By using a preformed nucleating centre we were able to obtain a single alloyed phase, which allowed us to address the synergistic effect to the presence of alloyed Au/Pd. The advantage of using this latter catalyst lies not only in the high activity but also in a prolonged catalyst life. Although a partial leaching of palladium and assembling of the particles have been revealed by ICP and HRTEM respectively, activity after 10 re-cycles decreased less than expected (about 10%).     

Genetic variants of human serum albumin in Italy: point mutants and a carboxyl-terminal variant

Of the > 50 different genetic variants of human serum albumin (alloalbumins) that have been characterized by amino acid or DNA sequence analysis, almost half have been identified in Italy through a long-term electrophoretic survey of serum. Previously we have reported structural studies of 11 Italian alloalbumins with point mutations, 2 different carboxyl-terminal variants, and 1 case of analbuminemia in an Italian family. This article describes confirmation by DNA sequencing of mutations previously inferred from protein sequencing of 4 of the above alloalbumins; it also reports the mutations identified by protein and DNA sequence analysis of 4 other Italian alloalbumins not previously recorded: albumin Larino, His3-->Tyr; Tradate-2 (protein sequencing only), Lys225-->Gln; Caserta, Lys276-->Asn; and Bazzano, a carboxyl-terminal variant. The first 3 have point mutations that produce a single amino acid substitution, but a nucleotide deletion causes a frameshift and an altered and truncated carboxyl-terminal sequence in albumin Bazzano. In these 4 instances the expression of the alloalbumin is variable, ranging from 10% to 70% of the total albumiN, in contrast to the usual 50% each for the normal and mutant albumin. The distribution of point mutations in the albumin gene is nonrandom; most of the 47 reported point substitutions involve charged amino acid residues on the surface of the molecule that are not concerned with ligand-binding sites.     

Characterization of a water-dispersible metal protective coating with Fourier transform infrared spectroscopy, modulated differential scanning calorimetry, and ellipsometry

An ethylene-methacrylic acid copolymer, formulated by BASF as a waterborne suspension of its alkylammonium salt and used, among other applications, in art conservation as a temporary protective coating was characterized using Fourier transform infrared (FT-IR) spectroscopy aided by modulated differential scanning calorimetry (MDSC) and ellipsometry. The thermal conversion of thin copolymer films from the freshly applied state, where carboxylic acid and carboxylate ion functional groups co-exist, to a purely acidic working state was spectroscopically followed. Transmission mid-infrared data of the working state showed a 1 : 12 ratio of methacrylic acid towards ethylene units. The glass transition temperature (T(g)) in the same state was found at 45 °C. Copolymer films spin-coated on mechanically polished bronze and iron coupons were characterized with transflection infrared spectroscopy and compared to corresponding transmission mid-infrared spectra of copolymer films spin-coated on silicon wafers. In the case of bronze coupons, evidence for interaction of the carboxylate ion with the copper substrate was obtained. The chemical structure and the thermal behavior of the coating, as well as some implications on its protective capability towards iron and copper alloys, is discussed as this material has received considerable attention in the field of metal conservation and coatings.     

Synthesis of water-soluble polymers containing sulfonic acid and amine moieties for the recovery of metal ions using ultrafiltration

Copolymers from 2-acrylamido-2-methyl-propane sulfonic acid (APSA) and N-acryloyl-N-methyl piperazine (AP) were synthesized by radical polymerization with ammonium peroxydisulfate as the initiator. The copolymerization yield ranged between 93 and 95%. The copolymers were completely water soluble, and were characterized by FTIR and NMR spectroscopy. The copolymer composition was determined from elemental analysis through the S/C ratio. The binding capacity for metal ion was studied by the LPR technique at different pH and filtration factors. The retention depended strongly on the pH and on the copolymer composition. With increasing pH and increasing content of APSA units in the copolymer, the metal ion retention increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 22–30, 2001     

Control structure synthesis for operational optimization of mixed refrigerant processes for liquefied natural gas plant

The best control structures for the energy optimizing control of propane precooled mixed refrigerant (C₃MR) processes were examined. A first principles‐based rigorous dynamic model was developed to analyze the steady‐state and dynamic behaviors of the C₃MR process. The steady‐state optimality of the C₃MR process was then examined in a whole operation space for exploring the feasibility of the energy optimizing control for possible control structures. As a result, the temperature difference (TD) between the warm‐end inlet and outlet MR streams was exploited as a promising controlled variable to automatically keep the liquefaction process close to its optimum. The closed‐loop responses were finally evaluated for every possible control structure candidate. Based on the steady‐state optimality and the dynamic performance evaluation, several control structures with a TD loop were proposed to be most favorable for the energy optimizing control of the C₃MR process. The proposed optimality approach can be applied to any natural gas liquefaction process for determining a proper controlled variable for optimizing operation. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2428–2441, 2014     

Effect of Particle Size on Monometallic and Bimetallic (Au,Pd)/C on the Liquid Phase Oxidation of Glycerol

The influence of metal particle size of monometallic and bimetallic supported catalysts (Au, Pd, Au–Pd)/C was studied using as a model reaction the liquid phase oxidation of glycerol. By tuning the metal particle size from 2 to 16 nm a progressive decrease of activity and simultaneously an increase in the selectivity to sodium glycerate was observed. Moreover, the influence of the temperature was studied and it was found that by increasing the temperature, only with a large particle size the formed glycerate was retained and not over-oxidized to tartronate.     

Synthesis,structural and morphological characteristics,magnetic and optical properties of Co doped ZnO nanoparticles

Zn_1−xCo_xO (x==0.05, 0.10, 0.15) nanoparticles have been synthesized by an alternative wet-chemical synthesis route using the SimAdd technique. The as-obtained powders were investigated by FT-IR spectroscopy, X-ray diffraction and thermal analysis correlated with evolved gas analysis (TG–DTA–FT-IR) in order to determine their chemical nature, crystalline structure and to establish the decomposition sequences. The precipitates are generally amorphous, but low-intensity reflection peaks assigned both to the zinc oxalate dihydrate, and zinc hydroxide can be observed in the recorded patterns, indicating that hydroxy-oxalate precipitates were obtained. The structure, morphology and magnetic properties of the thermally treated samples have been investigated by X-ray diffraction, FT-IR, HRTEM, SAED, UV–vis and EPR. XRD studies reveal a hexagonal wurtzite-type structure for all Zn_1−xCo_xO samples. TEM investigations show particle size between 28 and 37 nm, with spherical and polyhedral shapes and with tendency to form aggregates. The presence of a Co₃O₄ secondary phase was evidenced by XRD, UV–vis and EPR for the Zn_0.85Co_0.15O sample. The ferromagnetic behavior of the samples was revealed. The paper highlights that by varying the cobalt concentration it is possible to modulate the structural, morphological, optical and magnetic properties.     

Environmental and individual exposure to secondhand aerosol of electronic cigarettes in confined spaces: Results from the TackSHS Project†

Secondhand electronic cigarette (e-cigarette) aerosol (SHA) might impair indoor air quality and expose bystanders. This study aims to investigate exposure to SHA in controlled conditions of enclosed settings simulating real-world scenario. An experiment was performed in a car and in a room, in which SHA was generated during a 30-minute ad libitum use of an e-cigarette. The experiment was replicated on five consecutive days in each setting. We measured PM_2.5, airborne nicotine concentrations, and biomarkers of exposure to SHA, such as nicotine metabolites, tobacco-specific nitrosamines, propylene glycol, and glycerol in bystanders’ saliva samples before, during, and after the exposure period. Self-reported health symptoms related to exposure to SHA were also recorded. The results showed that the highest median PM_2.5 concentration was recorded during the exposure period, being 21 µg/m³ in the room setting and 16 µg/m³ in the car setting—about twofold increase compared to the baseline. Most concentrations of the airborne nicotine and all biomarkers were below the limit of quantification in both settings. Bystanders in both settings experienced some short-term irritation symptoms, expressed as dry throat, nose, eyes, and phlegm. In conclusion, short-term use of an e-cigarette in confined spaces increased indoor PM_2.5 level and caused some irritation symptoms in bystanders.