Quick supramolecular solvent-based microextraction for quantification of low curcuminoid content in food

There is a need to monitor the consumption of curcuminoids, an EU-permitted natural colour in food, to ensure that acceptable daily intakes are not exceeded, especially by young children. This paper describes a sensitive method able to quantify low contents of curcumin (CUR), demethoxycurcumin (DMC) and bis-demethoxycurcumin (BDMC) in foodstuffs. The method was based on a single-step extraction by use of a supramolecular solvent (SUPRAS) made up of reverse aggregates of decanoic acid, and direct analysis of the extract by use of liquid chromatography–photodiode array (PDA) detection. The extraction involved the stirring of 200 mg foodstuff with 600 μL SUPRAS for 15 min. No cleanup or concentration of the extracts was required. Curcuminoid solubilisation occurred via dispersion and hydrogen bonding. The method was used for the determination of curcuminoids in different types of foodstuff (snack, gelatine, yoghurt, mayonnaise, butter, candy and fish products) that encompassed a wide range of protein, fat, carbohydrate, sugar and water contents (0.85–11.04, 0–81.11, 0.06–75, 0.06–79.48, and 10.08–85.10 g, respectively, in each 100 g of food). Method quantification limits for the foodstuffs analysed were in the ranges 2.9–7.7, 2.8–11.2 and 3.3–9.0 μg kg^?1 for CUR, DMC and BDMC, respectively. The concentrations of curcuminoids detected in the foodstuffs and the recoveries obtained from fortified samples were in the ranges ND–284, ND–201 and ND–61.3 μg kg^?1, and 82–106, 89–106 and 90–102 %, for CUR, DMC and BDMC, respectively. The relative standard deviations were in the range 2–7 %. This method enabled quick and simple microextraction of curcuminoids with minimal solvent consumption, while delivering accurate and precise data.

The impact of an out‐of‐school STEM education program on students’ attitudes toward STEM and STEM careers

There is an increasing awareness of out‐of‐school program value in enhancing student interest and understanding of science, technology, engineering, and mathematics (STEM). This study examined the impact of an out‐of‐school STEM education program on student attitudes toward STEM disciplines and STEM careers. A STEM education program implemented at a public research university was designed to integrate STEM disciplines with hands‐on problem‐based activities. Design features included authentic learning contexts, engineering design processes, and content integration. Data sources included an attitude survey and interviews conducted with forty sixth grade middle school student participants. The analysis revealed significant differences between pre and posttests on student attitudes toward personal and social implications of STEM, science and engineering learning, and their relationship to STEM. Findings showed that the program contributed to students’ developing interest in STEM fields, and helped them make connections between schoolwork and daily lives. Recommendations for future research on out‐of‐school STEM education programs were discussed.     

Thermodynamic Data for the Formation of 1:1 and 2:1 Complexes of α,ω-Diamino Dihydrochlorides with 18-Crown-6 in Aqueous Solution

Calorimetric titrations are used to study the interactions between the crown ether 18-crown-6 and several α,ω-diamino dihydrochlorides in aqueous solution. These complexes are formed by ion-dipole interactions between the positively charged nitrogen atoms and the oxygen donor atoms of the crown ether. Depending on the experimental conditions, the formation of 1:1 or 2:1 complexes (ligand:diamines) can be studied. The solvation of the ligand and the amines are responsible for the observed thermodynamic values. The number of water molecules released during the reaction were calculated from the determined reaction entropies. Formation of 1:1 complexes distorts the solvation shell around the molecules. As a result, the number of solvent molecules released during the formation of the 2:1 complexes is slightly smaller than the number released from formation of the 1:1 complex. No experimental evidence is observed for the formation of complexes between one crown ether and two protonated amino groups.     

Solid-liquid interfacial energy of neopentylglycol

The grain boundary groove shapes for equilibrated solid neopentylglycol (2,2-dimethyl-1,3-propanediol) (NPG) with its melt were directly observed by using a horizontal temperature gradient stage. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient (Gamma), solid-liquid interfacial energy (sigma(SL)), and grain boundary energy (sigma(gb)) of NPG have been determined to be (7.4+/-0.7)x10(-8) Km, (7.9+/-1.2)x10(-3) Jm(-2), and (15.4+/-2.5)x10(-3) Jm(-2), respectively. The ratio of thermal conductivity of equilibrated liquid phase to solid phase for the NPG has also been measured to be 1.07 at the melting temperature.     

Metal ion complexation in acetonitrile by di-ionized calix[4]arenes bearing two dansyl fluorophores

The influence of metal cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ag⁺, Cd²⁺, Co²⁺, Fe²⁺, Hg²⁺, Mn²⁺, Pb²⁺, Zn²⁺ and Fe³⁺) on the spectroscopic properties of two dansyl (1-dimethylaminonaphthalene-5-sulfonyl) groups linked to the lower rims of a series of three, structurally related, di-ionized calix[4]arenes was investigated by means of absorption and emission spectrophotometry. Di(tetramethylammonium) salts of the di-ionized ligands, (TMA)₂L1, (TMA)₂L2 and (TMA)₂L3, which differ in having zero, two and four tert-butyl groups, respectively, on the upper rim of the calix[4]arene scaffold were utilized for the spectrofluorimetric titration experiments in acetonitrile. On complexation by alkaline earth metal cations, both the absorption and emission spectra undergo marked red shifts and quenching of the dansyl fluorescence. These effects are weaker with alkali metal cations. Transition metal cations interact strongly with the ligands. In particular, Fe³⁺, Hg²⁺ and Pb²⁺ cause greater than 97% quenching of the dansyl fluorescence in the di-ionized ligands.     

Metal Complexation Properties of Schiff Bases Containing 1,3,5-Triazine Derived from 2-Hydroxy-1-Naphthaldehyde in Solution. A Simple Spectrofluorimetric Method to Determine Mercury (II)

Four new Schiff base ligands carrying naphthalene groups were prepared from the reaction of 2,4-diamino-6-methyl-1,3,5-triazine and 2,4-diamino-6-undecyl-1,3,5-triazine with 2-hydroxy-1-naphthaldehyde. The influence of a series of metal ions including Cu²⁺, Co²⁺, Hg²⁺, Al³⁺, Cr³⁺, Fe³⁺, Pb²⁺, Ni²⁺, Cd²⁺, Zn²⁺, Mn²⁺, Ag⁺, Ba²⁺, Ca²⁺ and Mg²⁺ on the spectroscopic properties of the ligands was investigated by means of absorption and emission spectrometry. The results of spectrophotometric and spectrofluorimetric titrations disclosed the complexation stoichiometry and complex stability constant of the ligands with metal ions. A simple spectrofluorimetric method was developed using the Schiff base derived from 2,4-diamino-6-undecyl-1,3,5-triazine to determine Hg²⁺ ion. No cleanup or enrichment of the tap water sample was required. A modified standard addition method was used to eliminate matrix effect. The standard addition graph was linear between 0.2 and 2.6 mg/L in determination of Hg²⁺. Detection and quantification limits were 0.08 and 0.23 mg/L, respectively. The simple and cost-effective method can be applied to water samples.     

Cross‐coupling reactions in water using ionic liquid‐based palladium(II)–phosphinite complexes as outstanding catalysts

Two new phosphinite ligands based on ionic liquids [(Ph₂PO)C₇H₁₄N₂Cl]Cl ( 1 ) and [(Cy₂PO)C₇H₁₄N₂Cl]Cl ( 2 ) were synthesized by reaction of 1‐(3‐chloro‐2‐hydoxypropyl)‐3‐methylimidazolium chloride, [C₇H₁₅N₂OCl]Cl, with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, respectively, in anhydrous CH₂Cl₂ and under argon atmosphere. The reactions of 1 and 2 with MCl₂(cod) (M = Pd, Pt; cod = 1,5‐cyclooctadiene) yield complexes cis‐[M([(Ph₂PO)C₇H₁₄N₂Cl]Cl)₂Cl₂] and cis‐[M(Cy₂PO)C₇H₁₄N₂Cl]Cl)₂Cl₂], respectively. All complexes were isolated as analytically pure substances and characterized using multi‐nuclear NMR and infrared spectroscopies and elemental analysis. The catalytic activity of palladium complexes based on ionic liquid phosphinite ligands 1 and 2 was investigated in Suzuki cross‐coupling. They show outstanding catalytic activity in coupling of a series of aryl bromides or aryl iodides with phenylboronic acid under the optimized reaction conditions in water. The complexes provide turnover frequencies of 57 600 and 232 800 h^?1 in Suzuki coupling reactions of phenylboronic acid with p‐bromoacetophenone or p‐iodoacetophenone, respectively, which are the highest values ever reported among similar complexes for Suzuki coupling reactions in water as sole solvent in homogeneous catalysis. Furthermore, the palladium complexes were also found to be highly active catalysts in the Heck reaction affording trans‐stilbenes. Copyright © 2014 John Wiley & Sons, Ltd.