Uncertainty propagation through correction methodology for the determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry

Determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry (ICP-QMS) shows several spectroscopic overlaps from M⁺, MO⁺ and MOH⁺ ions. Especially, the spectroscopic interferences are observed from the atomic and molecular species of lighter rare earth elements including Ba during the determination of Eu, Gd and Tb. Mathematical correction methods, knowing the at.% abundances of different interfering isotopes, and the extent of formation of molecular species determined experimentally, have been used to account for various spectroscopic interferences. However, the uncertainty propagated through the mathematical correction limits its applicability. The uncertainty propagation increases with the increase in contribution from interfering species. However, for the same extent of total contribution, the overall error decreases when the interfering species are more than one. In this work, chondrite as well as a few geological reference materials containing different proportions of various rare earth elements have been used to study the contributions of different interfering species and the corresponding uncertainty in determining the concentrations of rare earth elements. A number of high abundant isotopes are proposed for determining the concentrations of various rare earth elements. The proposed isotopes are tested experimentally for determining the concentrations of different rare earth elements in two USGS reference materials AGV-1 and G-2. The interferences over those isotopes are corrected mathematically and the uncertainties propagated due to correction methodology are determined for those isotopes. The uncertainties in the determined concentrations of rare earth elements due to interference correction using the proposed isotopes are found to be comparable with those obtained by the commonly used isotopes for various rare earth elements.     

Contact-electro-catalysis for Direct Synthesis of H2O2 under Ambient Conditions

Hydrogen peroxide (H₂O₂) is an indispensable basic reagent in various industries, such as textile bleach, chemical synthesis, and environmental protection. However, it is challenging to prepare H₂O₂ in a green, safe, simple and efficient way under ambient conditions. Here, we found that H₂O₂ could be synthesized using a catalytic pathway only by contact charging a two-phase interface at room temperature and normal pressure. Particularly, under the action of mechanical force, electron transfer occurs during physical contact between polytetrafluoroethylene particles and deionized water/O₂ interfaces, inducing the generation of reactive free radicals (⋅OH and ⋅O₂⁻ ), and the free radicals could react to form H₂O₂, yielding as high as 313 μmol L⁻¹ h⁻¹. In addition, the new reaction device could show long-term stable H₂O₂ production. This work provides a novel method for the efficient preparation of H₂O₂, which may also stimulate further explorations on contact-electrification-induced chemistry process.     

Magnetic nanoparticle supported amine: An efficient and environmental benign catalyst for versatile Knoevenagel condensation under ultrasound irradiation

Amine functionalized silica coated Fe₃O₄ nanoparticles (SiO₂@MNP-A) were successfully prepared as a novel heterogeneous amine. The catalyst was characterized by XRD, FT-IR, TEM, magnetic measurement, elemental analysis and was found to be a magnetically separable and highly active catalyst for ambient Knoevenagel condensation of aromatic aldehydes and α-aromatic (heteroaromatic or polyaromatic)-substituted methylene compounds in water under ultrasonic irradiation to afford the corresponding products in good to excellent yields. Very interestingly, SiO₂@MNP-A successfully catalyze the reaction of the non-cyano substituted compound with benzaldehyde to achieve a key intermediate for the preparation of Atorvastatin calcium in green and atom-economic manner. In addition, the catalyst SiO₂@MNP-A can be reused for 8 times without any obvious loss of its activity. The role of ultrasonication in the Knoevenagel condensation was also discussed with the assistance of UV–vis spectrometry.     

Copper complex immobilized on imidazolium supported ionic liquid for ultrasound promoted ester synthesis

1-glycyl-3-methyl imidazolium chloride-copper (II) complex [[Gmim]Cl-Cu (II)] was found to be a heterogeneous catalyst for an efficient and greener solvent free synthesis of esters by condensation of carboxylic acids and alcohols with excellent yield with high turnover number (8.3 × 10² to 9.5 × 10²) using ultrasound irradiation. In addition, this method features reusability of catalyst, reduced waste, thus making new protocol more environmentally suitable whilst no catalyst leaching was observed.     

Preparation of betulinic acid nanoemulsions stabilized by ω-3 enriched phosphatidylcholine

Bioactive compounds such as ω-3 fatty acids and terpenes, have been associated with beneficial health effects; however, their solubility in the gastrointestinal tract and its bioavailability in the body are low. Nanoemulsions offer a viable alternative to disperse lipophilic compounds and improve their dissolution, permeation, absorption and bioavailability. Enzyme modified phosphatidylcholine (PC) with ω-3 fatty acids was used as emulsifier to stabilize oil-in-water nanoemulsions generated using ultrasound device. These systems were used as carriers of betulinic acid, which has reported anti-carcinogenic activity. Phospholipase-catalyzed modification of PC allowed the incorporation of 50 mol% of ω-3 fatty acids. Formation variables such as oil type and ultrasound amplitude had effects on nanoemulsion characteristics. Incorporation of betulinic acid affected globule size; however, betulinic acid nanoemulsions below 200 nm could be prepared. The conditions under which betulinic acid nanoemulsions were obtained using the modified phosphatidylcholine with the smaller globule size (91 nm) were 10% PC, 25% glycerol, medium chain oil and 30% amplitude for 12 min in the sonicator. Storage temperature had an effect on the stability of the nanoemulsions, at 5 °C we observed the smallest growth in globule size. The use of olive oil decreased the globule size growth during storage of the nanoemulsion stabilized with modified phosphatidylcholine, although globule size obtained was greater than 200 nm. Medium pH had a significant effect on the nanoemulsions; alkaline pH values improved storage stability. These results provide useful information for using this type of carrier system on the formulation of products in the pharmaceutical or food industry.     

High regioselective ultrasonic-assisted synthesis of 2,7-diaryl-4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids

New and high regioselective method of the synthesis of 2,7-diaryl-4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids by reaction of 3-aryl-5-aminopyrazoles with arylidenpyruvic acid at room temperature under ultrasonication was developed and discussed.     

Enhancement of enzymatic digestion of Antarctic krill and successive extraction of selenium organic compounds by ultrasound treatment

In a previous work we described the isolation of selenium organic species from Antarctic krill after enzymatic hydrolysis. In this paper we present the results of the influence of ultrasonication on the enzymatic treatment and the successive isolation of selenomethionine. We showed that ultrasound-assisted enzymatic digestion leads to quantitative release of selenium in the soluble fraction and recovery of selenomethionine from the krill protein within a time 2 orders of magnitude shorter. The solubilised sample was analysed by size-exclusion chromatography and the selenomethionine content was quantified by high-performance liquid chromatography–inductively coupled plasma mass spectrometry. In total, 99% of the selenomethionine in the krill hydrolysate was recovered from the chromatographic fractions. It corresponds to 35% of the total selenium content in Antarctic krill. Monitoring by microscopy of the changes in the structure of the krill samples during ultrasonication suggested that the enhancement of the ultrasound-assisted enzymatic reaction was mainly due to decrease of mass transfer limitations. A reference experiment for ultrasound-assisted enzymatic digestion of cell-free protein in a homogeneous system does not exclude direct influence of the ultrasound energy on the enzyme–substrate interaction.     

Facile preparation of superhydrophobic copper surface by HNO3 etching technique with the assistance of CTAB and ultrasonication

Superhydrophobic rough structure was prepared on copper wafer via HNO₃ etching technique with the assistance of Cetyltrimethyl Ammonium Bromide (CTAB) and ultrasonication. After modification of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FDTES), the copper wafer showed stable superhydrophobicity. The morphologies, chemical compositions and hydrophobicity of the substrates were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. Dense and spherical micropits appeared on copper wafer after it was etched by 5 M nitric acid with 1.2 mM CTAB under ultrasonication for 20 min. The SEM results indicated that the joint action of CTAB and ultrasonication caused the formation of dense and spherical micropits.     

Ultrasound‐assisted magnetic SPE based on Fe3O4‐grafted graphene for the determination of polychlorinated biphenyls in water samples

An ultrasound‐assisted magnetic SPE procedure with an Fe₃O₄‐grafted graphene nanocomposite as the magnetic adsorbent has been developed to determine seven polychlorinated biphenyls (PCBs; PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB180) simultaneously in 200 mL environmental water samples, in combination with GC–MS/MS. Several factors related to magnetic SPE efficiencies, such as the superparamagnetic intensity and amount of adsorbent, extraction time, sample pH, and desorption conditions were investigated. With the assistance of ultrasound, the extraction achieved the maximum within only 20 s, attributed to the powerful adsorptive ability of the magnetic adsorbent toward the PCBs. Under the optimized conditions, an excellent linearity was observed in the range of 0.1–100 ng/L for PCB28, 0.2–100 ng/L for PCB52, and 0.5–100 ng/L for the other five PCBs with the correlation coefficients ranging from 0.9988 to 0.9996. The mean recoveries at spiked levels of 5.0 and 10.0 ng/L were 84.9–108.5%, the coefficients of variations were <6.5%. With convenient magnetic separation, the synthesized magnetic adsorbent could be recycled more than ten times. The proposed method was demonstrated to be feasible, simple, rapid, and easy to operate for the trace analysis of the PCBs in environmental water samples.     

A novel strategy for producing nano-particles from date seeds and enhancing their phenolic content and antioxidant properties using ultrasound-assisted extraction: A multivariate based optimization study

Date seeds from the date palm fruit are considered as a waste and they are known to contain several bioactive compounds. Producing nanoparticles from the date seeds can enhances their effectiveness and their utilization as novel functional food ingredients. In this study, date seed nanoparticles (DSNPs) synthesized using acid (HCl) hydrolysis method (HCl concentration of 38% and hydrolysis time of 4 days) was found to have particle size between 50 and 150 nm. The obtained DSNPs were characterized by measuring particle size and particle charge (Zetasizer), morphology using scanning electron microscope (SEM), and determination of the functional groups using fourier-transform infrared spectroscopy (FTIR). DSNPs were further treated with green extraction technology [ultrasound-assisted extraction (UAE)] using water-based and methanol-based solvent for optimizing the extraction of the bioactive compounds by implementing response surface methodology (RSM). The UAE of DSNPs were analysed for set of responses including total phenolic content (TPC), total flavonoid content (TFC), 1,1-diphenyl-2-picrlthydrazyl (DPPH) radical scavenging activity, ferric ion reducing antioxidant power (FRAP), and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical scavenging activity. Three-factor and four-factor Box-Behnken design (BBD) of three models (Synthesis of DSNPs, UAE with water, and UAE with methanol) was performed. The results showed that in UAE of DSNPs using water-based solvent, the key independent factors effecting the TPC and TFC and antioxidant activities were S:L ratio (40:1 mg/ml) and treatment time (9 min). Whereas the methanol-based UAE of DSNPs was mostly affected by US amplitude/power (90%) and methanol concentration (80%). All models were further optimized using response optimizer in Minitab and the generated predicted values were very comparable to the actual obtained results which confirm the significance and validity of all RSM models used. The phenolic compounds identified from DSNPs consisted mainly of 3,4-Dihydroxy benzoic acid, ferulic acid, and p-coumaric acid. The present study demonstrated a successful method for synthesising DSNPs as well as documented the optimum UAE conditions to maximize the extraction of polyphenolic compounds from DSNPs and enhancing their antioxidant activities to be used in food application.