Biphasic kinetic investigations on the evaluation of non-salt forming reductants for Pu(IV) stripping from tributyl phosphate and N,N-dihexyl octanamide solutions in n-dodecane

The relative stability of different oxidation states of actinide elements is influenced by the nature of complexes formed and redox equilibria in aqueous/non-aqueous solutions. The reduction/stripping studies on Pu(IV) ions from loaded organic phases of 1.1 M tributyl phosphate and of 1.1 M N,N-dihexyl octanamide in n-dodecane were studied using organic soluble tert-butyl hydroquinone (TBH) and aqueous soluble reductants like acetaldoxime (AX) and hydroxyurea (HU). These studies were carried out as a function of reductant and nitric acid concentration (0.5–4 M HNO₃) and of time. The changes in Pu oxidation states were followed by spectrophotometry for TBH and by distribution ratio values for AX and HU as reductants. Spectrophotometric investigations using TBH as reductant showed that it was desirable to strip Pu(III) formed after reduction of Pu(IV) in the organic phase, which may otherwise be reconverted to extractable Pu(IV) by in situ generated HNO₂ from oxidative degradation of TBH to tert-butyl quinone. Similarly, the biphasic reduction/stripping of Pu(IV) using AX and HU as reductant rate was affected adversely with increased aqueous phase acidity. This data will help in the accurate simulation of Pu separation processes using these reductants in mixer-settlers/pulsed columns or centrifugal contactors.     

N,N-Dialkyl amides as extractants for spent fuel reprocessing: an overview

Reprocessing of spent nuclear fuel is vital for the long-term global nuclear power growth and is the major motivation for developing novel separation schemes. Conventionally, PUREX and THOREX processes have been proposed for the reprocessing of U and Th based spent fuels employing tri-n-butyl phosphate (TBP) as extractant. However, based on the experiences gained over last five–six decades on the reprocessing of spent fuels, some major drawbacks of TBP have been identified. Evaluation of alternative extractants is, therefore, desirable which can overcome at least some of these problems. Extensive studies have been carried out on the evaluation of N,N-dialkyl amides as extractants in the back-end of the nuclear fuel cycle for addressing the issues related to the reprocessing of U and Th based spent fuels. Under advanced fuel cycle scenario, efforts are also being made by countries with a developed nuclear technological base to provide safe nuclear power to other countries and to minimize proliferation concerns worldwide. This paper presents an overview of studies carried out in our laboratory on different aspects of reprocessing of U and Th based spent fuels employing N,N-dialkyl amides as extractants.     

Aliphatic Amine Discrimination by Pentafluorophenyl Dibromo BODIPY

Two new fluorescent BODIPY dyes have been designed and synthesized. They dyes differ in their meso substituents, which have different electronic properties. Their selective reactivity towards an Ar‐S_N2 reaction has been explored as a potential basis for colorimetric and fluorescent discrimination of primary, secondary and tertiary aliphatic amines. This dual‐mode, instantaneous recognition event is unprecedented.     

A simple and cost-effective synthesis of sulfated β-cyclodextrin and its application as chiral mobile phase additive in the separation of cloperastine enantiomers

Journal of Inclusion Phenomena and Macrocyclic Chemistry - A simple and cost-effective method for the synthesis of sulfated β-cyclodextrin, one of the most widely used chiral mobile phase...     

Rotary disc bioreactor-based approach for bacterial nanocellulose production using Gluconacetobacter xylinus NCIM 2526 strain

Bacterial nanocellulose (BNC) is an indomitable biomaterial of utmost usage in different technological areas. Previously, the BNC production has been reported in the simplified bioreactors. Thus, pioneering bioreactor-assisted strategies are desirable for the commendable BNC production. Advanced bioreactors must be corroborated along with different bacterial strains to obtain creditable BNC yield. This study deals with BNC production in rotary disc bioreactor (RDBR) using Gluconacetobacter xylinus NCIM 2526 strain. RDBR-based production of BNC provided 189?±?14 gL^?1 of wet BNC, i.e., equivalent to 6.6?±?0.3 gL^?1 dry BNC yield in 10 days. However, in static cultivation mode, 56?±?12 gL^?1 wet weight of BNC, corresponding to 2.4?±?0.4 gL^?1 dry weight, was produced. Thus, BNC production was approximately 2.75 folds higher in RDBR than statically produced BNC from the same volume of the media. The sugar to BNC conversion yield (12.2?±?0.8%) was doubled in RDBR-based production as compared to static BNC production (6.2?±?1.4%) with efficient sugar consumption (90.0?±?3.3%). The maximum amount of BNC was produced at 7 RPM and pH 6. RDBR-based BNC showed a more hydrophilic nature than statically produced BNC. The RDBR might be appropriate for large-scale BNC production, especially for wet-end applications, as an ample amount of BNC can be produced from a single fermentation process. These BNC pellicles might have the potential for biomedical applications like wound dressings, biofacial masks, hydrogels, and tissue engineering scaffolds.

     

Evaluation of novel ZnO–Ag cathode for CO2 electroreduction in solid oxide electrolyser

CO₂ and steam/CO₂ electroreduction to CO and methane in solid oxide electrolytic cells (SOEC) has gained major attention in the past few years. This work evaluates, for the very first time, the performance of two different ZnO–Ag cathodes: one where ZnO nanopowder was mixed with Ag powder for preparing the cathode ink (ZnO_mix–Ag cathode) and the other one where Ag cathode was infiltrated with a zinc nitrate solution (ZnO_inf –Ag cathode). ZnO_mix–Ag cathode had a better distribution of ZnO particles throughout the cathode, resulting in almost double CO generation while electrolysing both dry CO₂ and H₂/CO₂ (4:1 v/v). A maximum overall CO₂ conversion of 48% (in H₂/CO₂) at 1.7 V and 700 °C clearly indicated that as low as 5 wt% zinc loading is capable of CO₂ electroreduction. It was further revealed that for ZnO_inf –Ag cathode, most of CO generation took place through RWGS reaction, but for ZnO_mix–Ag cathode, it was the synergistic effect of both RWGS reaction and CO₂ electrolysis. Although ZnO_inf –Ag cathode produced trace amount of methane at higher voltages, with ZnO_mix–Ag cathode, there was absolutely no methane. This seems to be due to strong electronic interaction between Zn and Ag that might have suppressed the catalytic activity of the cathode towards methanation.

     

Monitoring the Reaction of the Body State to Antibiotic Treatment against Helicobacter pylori via Infrared Spectroscopy: A Case Study

The current understanding of deviations of human microbiota caused by antibiotic treatment is poor. In an attempt to improve it, a proof-of-principle spectroscopic study of the breath of one volunteer affected by a course of antibiotics for Helicobacter pylori eradication was performed. Fourier transform spectroscopy enabled searching for the absorption spectral structures sensitive to the treatment in the entire mid-infrared region. Two spectral ranges were found where the corresponding structures strongly correlated with the beginning and end of the treatment. The structures were identified as methyl ester of butyric acid and ethyl ester of pyruvic acid. Both acids generated by bacteria in the gut are involved in fundamental processes of human metabolism. Being confirmed by other studies, measurement of the methyl butyrate deviation could be a promising way for monitoring acute gastritis and anti-Helicobacter pylori antibiotic treatment.     

Comparison of Three Plasma Sources for Ambient Desorption/Ionization Mass Spectrometry

Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources. Figure

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Characterization of multiple fragmentation pathways initiated by collision‐induced dissociation of multifunctional anions formed by deprotonation of 2‐nitrobenzenesulfonylglycine

The correlation of anion structure with the fragmentation behavior of deprotonated nitrobenzenesulfonylamino acids was investigated using tandem mass spectrometry, isotopic labeling and computational methods. Four distinct fragmentation pathways resulting from the collision‐induced dissociation (CID) of deprotonated 2‐nitrobenzenesulfonylglycine (NsGly) were characterized. The unusual loss of the aryl nitro substituent as HONO was the lowest energy process. Subsequent successive losses of CO, HCN and SO₂ indicated that an ortho cyclization reaction had accompanied loss of HONO. Other pathways involving rearrangement of the ionized sulfonamide group, dual bond cleavage and intramolecular nucleophilic displacement were proposed to account for the formation of phenoxide, arylsulfinate and arylsulfonamide product ions at higher collision energies. The four distinct fragmentation pathways were consistent with precursor–product relationships established by CID experiments, isotopic labeling results and the formation of analogous product ions from 2,4‐dinitrobenzenesulfonylglycine and the Ns derivatives of alanine and 2‐aminoisobutyric acid. The computations confirmed a low barrier for ortho cyclization with loss of HONO and feasible energetics for each reaction step in the four pathways. Computations also indicated that three of the fragmentation pathways started from NsGly ionized at the carboxyl group. Overall, the pathways identified for the fragmentation of the NsGly anion differed from processes reported for anions containing a single functional group, demonstrating the importance of functional group interactions in the fragmentation pathways of multifunctional anions. Copyright © 2014 John Wiley & Sons, Ltd.