Determination of carbonate in marine solid samples by FTIR-ATR spectroscopy

A method for detecting carbonate in marine solid samples (sediments, corals) by Fourier transform infrared spectroscopy (FTIR) coupled to the total attenuated reflectance (ATR) technique is described. Compared to other techniques, the proposed method is not based on the measurement of CO2 evolved by combustion or acidification of the sample, but on the direct measurement of carbonate present in the sample. For this reason, the method by FTIR-ATR spectroscopy does not require any chemical pre-treatment. The proposed method allows determination of carbonate in the range 6-100% (w/w) as Na2CO3 and gives comparable results with the determination of inorganic carbon by elemental analysis.     

Correction of the interference by mixing the reagents in the bioluminescent determination of ATP in environmental samples by an interfaced PC photometer and a robust regression procedure

 An automated procedure for correcting the interference due to mixing the reagents in the determination of ATP by a bioluminescent technique is described. The measurements were performed by an in-house interfaced PC photometer. An automated procedure based on a robust regression method and outliers detection was applied to exclude the time of the mixing of the reagents from the global time of reaction. In fact the mixing of the reagents is responsible of the poor analytical precision (RSD%>25) and low sensitivity (limit of detection≈2×10^-8 mol/l). By this procedure, the precision (RSD%<7) and sensitivity (limit of detection≈8×10^-10 mol/l) were improved. The method was applied to the determination of ATP in marine sediments and good recovery within 90–108% was obtained. For non-polluted samples the measurement can be carried out by direct comparison with standard solutions. The standard addition procedure is recommended for polluted samples. Received: 25 April 1996/Revised: 28 June 1996/Accepted: 3 July 1996     

Synthesis of H‐shaped complex macromolecular structures by combination of atom transfer radical polymerization,photoinduced radical coupling,ring‐opening polymerization,and iniferter processes

Three controlled/living polymerization processes, namely atom transfer radical polymerization (ATRP), ring‐opening polymerization (ROP) and iniferter polymerization, and photoinduced radical coupling reaction were combined for the preparation of ABCBD‐type H‐shaped complex copolymer. First, α‐benzophenone functional polystyrene (BP‐PS) and poly(methyl methacrylate) (BP‐PMMA) were prepared independently by ATRP. The resulting polymers were irradiated to form ketyl radicals by hydrogen abstraction of the excited benzophenone moieties present at each chain end. Coupling of these radicals resulted in the formation of polystyrene‐b‐poly(methyl methacrylate) (PS‐b‐PMMA) with benzpinacole structure at the junction point possessing both hydroxyl and iniferter functionalities. ROP of ε‐caprolactone (CL) by using PS‐b‐PMMA as bifunctional initiator, in the presence of stannous octoate yielded the corresponding tetrablock copolymer, PCL‐PS‐PMMA‐PCL. Finally, the polymerization of tert‐butyl acrylate (tBA) via iniferter process gave the targeted H‐shaped block copolymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4601–4607     

Ultrasound-assisted analysis of total carbohydrates in environmental and food samples.

Analytical methods to determine total carbohydrates in environmental and food samples usually require a preliminary chemical hydrolytic procedure to convert polysaccharides into monosaccharides prior to detection by colorimetric or chromatographic techniques. In this paper, an alternative hydrolytic procedure is presented. The method for hydrolysis of polysaccharides is based on the application of ultrasound at room temperature. The advantages of the method proposed here are reduced time required for analysis (4-5 h) and the improvement of the analytical accuracy due to the absence of the most common reactions of oxidation. The proposed method was applied to the determination of total carbohydrates in several environmental samples (seawater and marine mucilage) and starchy food samples. Results for total carbohydrate obtained using the ultrasound procedure for hydrolysis of samples agreed with those found when applying other published procedures.     

New eco-friendly low-cost binders for Li-ion anodes

In the production of commercial Li-ion batteries, the active materials slurries are generally prepared using polyvinylidene fluoride (PVdF) as binder because of its good adhesion properties and electrochemical stability. Unfortunately, there are some disadvantages related to the use of PVdF: the most important is the use of toxic and environmentally unfriendly solvents, such as N-methyl-pyrrolidone (NMP), and the second is the high costs. In the light of these considerations, it seemed straightforward to investigate the suitability of some water-soluble, inexpensive, and eco-friendly materials to test as alternative binders (sodium alginate, chitosan tragacanth gum, gelatin). The rheological properties of these materials have been investigated in addition to the electrochemical characterization. Furthermore, graphite electrodes with PVdF, carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR) binders have been considered for sake of comparison. We found that some of these water-soluble binders, besides good electrochemical performances, showed a high adhesion to the current collector and a good electrochemical stability under the experimental conditions employed, which makes them interesting for the next generation of Li-ion batteries.     

Micro-Mesoporous Carbons from Cyclodextrin Nanosponges Enabling High-Capacity Silicon Anodes and Sulfur Cathodes for Lithiated Si-S Batteries

Manufactured globally on industrial scale, cyclodextrins (CD) are cyclic oligosaccharides produced by enzymatic conversion of starch. Their typical structure of truncated cone can host a wide variety of guest molecules to create inclusion complexes; indeed, we daily use CD as unseen components of food, cosmetics, textiles and pharmaceutical excipients. The synthesis of active material composites from CD resources can enable or enlarge the effective utilization of these products in the battery industry with some economical as well as environmental benefits. New and simple strategies are here presented for the synthesis of nanostructured silicon and sulfur composite materials with carbonized hyper cross-linked CD (nanosponges) that show satisfactory performance as high-capacity electrodes. For the sulfur cathode, the mesoporous carbon host limits polysulfide dissolution and shuttle effects and guarantees stable cycling performance. The embedding of silicon nanoparticles into the carbonized nanosponge allows to achieve high capacity and excellent cycling performance. Moreover, due to the high surface area of the silicon composite, the characteristics at the electrode/electrolyte interface dominate the overall electrochemical reversibility, opening a detailed analysis on the behavior of the material in different electrolytes. We show that the use of commercial LP30 electrolyte causes a larger capacity fade, and this is associated with different solid electrolyte interface layer formation and it is also demonstrated that fluoroethylene carbonate addition can significantly increase the capacity retention and the overall performance of our nanostructured Si/C composite in both ether-based and LP30 electrolytes. As a result, an integration of the Si/C and S/C composites is proposed to achieve a complete lithiated Si−S cell.