Aqueous Surfactant Two‐Phase Systems for the Continuous Countercurrent Cloud Point Extraction

Aqueous nonionic surfactant solutions split into two phases if the temperature is increased beyond a certain temperature, the so‐called cloud point temperature. Presently many different types of nonionic surfactants are produced commercially, out of these numerous have been considered as potential solvent for the cloud point extraction. In this work the crucial thermophysical properties of nonionic surfactants are investigated to determine the potential of surfactant systems for extraction processes. Phase equilibria of the binary system Triton X‐114/water and the ternary system Triton X‐114/water/phenol were measured. Based on these data the cloud point extraction was implemented in a continuous stirred extraction column. It was found, that increasing temperature within the column reduces the loss of surfactant and leads to an increasing enrichment factor. This work demonstrates that surfactant/water systems represent a suitable alternative to conventional solvents and can effectively be processed in continuous extraction columns.     

Novel (phenylethynyl)pyrene-LNA constructs for fluorescence SNP sensing in polymorphic nucleic acid targets

We describe fluorescent oligonucleotide probes labeled with novel (phenylethynyl)pyrene dyes attached to locked nucleic acids. Furthermore, we prove the utility of these probes for the effective detection of single-nucleotide polymorphisms in natural nucleic acids. High-affinity hybridization of the probes and excellent fluorescence responses to single-base mismatches in DNA/RNA targets are demonstrated in model dual-probe and doubly labeled probe formats. This stimulated us to develop two diagnostic systems for the homogeneous detection of a drug-resistance-causing mutation in HIV-1 protease cDNA and RNA gene fragments. Target sequences were obtained by analysis of 200 clinical samples from patients currently receiving anti-HIV/AIDS combination therapy at the Russian Federal AIDS Center. Using these fluorescent oligonucleotides, we were able to detect the target mutation despite all the challenges of the natural targets, that is, the presence of additional mutations, neighboring sequence variation, and low target concentration, which typically reduce binding and effectiveness of sensing by fluorescent oligonucleotides.     

Molar mass-dependent profiles of functional groups and carbohydrates in kraft lignin

Technical lignins are complex, irregular, polyphenolic compounds obtained in large quantities as by-products of the pulp and paper industries or according to current biorefinery setups. The availability of kraft lignin is increasing due to larger scale retrieval from process liquors, which opens new possibilities for further refining or new applications of such lignins. In the present study, sequential ultrafiltration of kraft lignin was performed to fractionate the lignin and to elucidate molar mass-dependent changes in lignin structure. Two industrial black liquors and three precipitated lignins were fractionated, and their functional groups were determined, providing molar mass-dependent profiles. Interrelations between structural parameters and functional groups, the molecular weight ranges, and the different lignin sources are discussed. This will help to establish structure-property-application relationships (SPARs) for technical lignins which are required for any future large-scale application.     

In situ MAS NMR investigations of molecular sieves and zeolite-catalyzed reactions

Solid-state MAS NMR is a powerful technique to study heterogeneous catalysts and the way by which they operate. In situ MAS NMR has been demonstrated to be a powerful method to understand reaction mechanisms, to study the nature, dynamics and reactivity of surface intermediates and active sites, and to characterize structural modifications in the catalyst itself, in particular when using ¹³C strategically labelled substrates. In this paper, three examples selected from our own work are used to illustrate the potential of in situ MAS NMR. They are the formation of cumene and its isomerization to n-propylbenzene on zeolite H-ZSM-11, the activation of propane at low temperature and the alkylation of benzene with propane on zeolite H-ZSM-5, and the characterization of the aluminophosphate molecular sieve VPI-5 structure with temperature. Studies of the alkylation of benzene with propene confirmed that cumene was the primary reaction product. The undesired n-propylbenzene by-product results from the intermolecular reaction between cumene and benzene, enhanced by molecular shape-selective effects in medium pore size zeolites (e.g., H-ZSM-11). It explains why large pore zeolites, e.g., zeolite Beta, are used commercially today for this process. Propane can be activated at low temperature (ca. 573 K) on bifunctional medium pore size zeolites possessing intimately related acidic Brønsted sites and a dehydrogenation function provided by Ga or Zn species. In Ga/H-ZSM-5 catalysts, at 573 K, the activation of propane was shown to occur via a protonated pseudocyclopropane (PPCP) intermediate (or transition state). The latter evolves in a manner that can be formally described by the formation of CH ₃ ⁺ , C₂H ₂ ⁺ , and C₃H ₇ ⁺ carbenium ion intermediates. These species can react with olefins, alkanes, or other electron-rich molecules such as benzene. The primary reaction products of the reaction of propane with benzene are n-propylbenzene (in small amount), ethylbenzene and toluene. Their subsequent reactions lead eventually to toluene and xylenes as the final products. In the structural characterization of VPI-5, ²⁷Al, ³¹P, and ²⁷Al nutation MAS NMR spectra show that, at 294 K, fully hydrated VPI-5 contains three equally populated Al and P crystallographic sites and that one-third of Al is 6-coordinate. The VPI-5 structure then belongs to the P6₃ space group. Above 353 K, VPI-5, fully or partially hydrated, undergoes a structural transformation to a higher framework symmetry, i.e., the P6₃cm space group. The transformation occurs at nearly the same temperature in both cases, indicating that the breakdown of the hydrogen-bonded helical water structure inside the VPI-5 pores is not a factor in the process.     

Kinetics and mechanism of low-temperature ozone decomposition by Co-ions adsorbed on silica

Kinetics and mechanism of low-temperature ozone ((5–50) × 10⁻³ mol/m³ in the gas–air mixture) decomposition by Co-catalysts supported on silica have been studied. Co-ions adsorbed on silica react with surface oxygen species, thus resulting in an active catalyst. Low concentrations of Co-ions form a monolayer on the surface. Their specific catalytic activity remained constant, but sharply decreased at higher concentrations due to a formation of polynuclear Co-complexes. Ozone decomposition may occur either as a stoichiometric or catalytic process, depending on the ozone and catalyst concentrations. The turnover number increases with ozone concentration reaching a saturation point. It also increases with Co-concentration in the beginning, but drops at a concentration >1 × 10⁻⁴ mol/g. The mechanism of the reaction is discussed.