A magnetic MoS2-Fe3O4 nanocomposite as an effective adsorbent for dispersive solid-phase microextraction of lead(II) and copper(II) prior to their determination by FAAS

Microchimica Acta - The authors describe the preparation of a nanocomposite (mag-MoS2-Fe3O4) that was prepared from molybdenum disulfide (MoS2) and magnetic Fe3O4 nanoparticles by a hydrothermal...     

Reductive Decationizable Block Copolymers for Stimuli‐Responsive mRNA Delivery

Messenger ribonucleic acids (mRNAs) are considered as promising alternatives for transient gene therapy, but to overcome their poor pharmacokinetic properties, smart carriers are required for cellular uptake and stimuli‐responsive release. In this work, a synthetic concept toward reductive decationizable cationic block copolymers for mRNA complexation is introduced. By combination of RAFT block copolymerization with postpolymerization modification, cationic block copolymers are generated with disulfide‐linked primary amines. They allow effective polyplex formation with negatively charged mRNA and subsequent release under reductive conditions of the cytoplasm. In first in vitro experiments with fibroblasts and macrophages, tailor‐made block copolymers mediate cell‐specific mRNA transfection, as quantified by polyplex uptake and mRNA‐encoding gene expression. Furthermore, RAFT polymerization provides access to heterotelechelic polymers with orthogonally addressable endgroup functionalities utilized to ligate targeting units onto the polyplex‐forming block copolymers. The results exemplify the broad versatility of this reductive decationizable mRNA carrier system, especially toward further advanced mRNA delivery applications.

     

Hille’s non-oscillation theorem and the decay of solutions to a class of semi-linear PDE’s

With a change of perspective in Hille’s paper on oscillation [Trans. Amer. Math. Soc. 64 (1948), 234–252], we provide optimal integral conditions for an application of the method of sub-solutions and super-solutions to investigating the existence of solutions for the semi-linear elliptic equation in the euclidean space , n ≥ 3, that decay to zero as . Received: 26 October 2006     

Biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin

The biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin for preconcentration-separation of them have been investigated. The sorbed analytes on biosorbent were eluted by using 1 mol L⁻¹ HCl and analytes were determined by flame atomic absorption spectrometry. The influences of analytical parameters including amounts of pH, B. sphaericus, sample volume etc. on the quantitative recoveries of analytes were investigated. The effects of alkaline, earth alkaline ions and some metal ions on the retentions of the analytes on the biosorbent were also examined. Separation and preconcentration of Cu, Pb, Fe and Co ions from real samples was achieved quantitatively. The detection limits by 3 sigma for analyte ions were in the range of 0.20-0.75 μg L⁻¹ for aqueous samples and in the range of 2.5-9.4 ng g⁻¹ for solid samples. The validation of the procedure was performed by the analysis of the certified standard reference materials (NRCC-SLRS 4 Riverine Water, SRM 2711 Montana soil and GBW 07605 Tea). The presented method was applied to the determination of analyte ions in green tea, black tea, cultivated mushroom, boiled wheat, rice and soil samples with successfully results.     

Spectrophotometric determination of ascorbic acid by the modified CUPRAC method with extractive separation of flavonoids-La(III) complexes

The proposed method for ascorbic acid: AA (Vitamin C) determination is based on the oxidation of AA to dehydroascorbic acid with the CUPRAC reagent of total antioxidant capacity assay, i.e., Cu(II)-neocuproine (Nc), in ammonium acetate-containing medium at pH 7, where the absorbance of the formed bis(Nc)-copper(I) chelate is measured at 450 nm. The flavonoids (essentially flavones and flavonols) normally interfering with the CUPRAC procedure were separated with preliminary extraction as their La(III) chelates into ethylacetate (EtAc). The Cu(I)-Nc chelate responsible for color development was formed immediately with AA oxidation. Beer's law was obeyed between 8.0 × 10⁻⁶ and 8.0 × 10⁻⁵ M concentration range, with the equation of the linear calibration curve: A_450 nm = 1.60 × 10⁴C (mol dm⁻³) − 0.0596. The relative standard deviation (R.S.D.) in the analysis of N = 45 synthetic mixtures containing 1.25 × 10⁻² mM AA with flavonoids was 5.3%. The Cu(II)-Nc reagent is a lower redox-potential and therefore more selective oxidant than the Fe(III)-1,10-phenanthroline reagent conventionally used for the same assay. This feature makes the proposed method superior for real samples such as fruit juices containing weak reductants such as citrate, oxalate and tartarate that may otherwise produce positive errors in the Fe(III)-phen method when equilibrium is achieved. The developed method was applied to some commercial fruit juices and pharmaceutical preparations containing Vitamin C + bioflavonoids. The findings of the developed method for fruit juices and pharmaceuticals were statistically alike with those of HPLC. The proposed spectrophotometric method was practical, low-cost, rapid, and could reliably assay AA in the presence of flavonoids without enzymatic procedures open to interferences by enzyme inhibitors.     

Oxygen-18 measurement of Andalusian olive oils by continuous flow pyrolysis/isotope ratio mass spectrometry

We report a method for the determination of delta(18)O isotopic abundance in olive oils. The results obtained by applying the method to various Andalusian oil samples obtained in the 2004/05 and 2005/06 seasons are discussed in relation to olive variety, geographical origin, climate and ripeness index. Application of the method to samples of assured varietal purity exposed the influence of olive variety and origin but not of the ripeness index. The delta(18)O values for the 2005/06 season are higher on average than those obtained in the colder 2004/05 season. Results obtained for samples of the Picual and Hojiblanca varieties in Córdoba and Málaga in the 2005/06 season suggest a correlation between enrichment in heavy isotopes and latitude whereas no clear-cut effect of altitude was observed.     

Spectroscopic studies of charge transfer complexes between colchicine and some pi acceptors

Charge transfer complexes between colchicine as donor and pi acceptors such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), p-chloranil (p-CHL) have been studied spectrophotometrically in dichloromethane at 21 degrees C. The stoichiometry of the complexes was found to be 1:1 ratio by the Job method between donor and acceptors with the maximum absorption band at a wavelength of 535, 585 and 515 nm. The equilibrium constant and thermodynamic parameters of the complexes were determined by Benesi-Hildebrand and van't Hoff equations. Colchicine in pure form and in dosage form was applied in this study. The formation constants for the complexes were shown to be dependent on the structure of the electron acceptors used.     

Contents of selected B vitamins in NIST SRM 3280 multivitamin/multielement tablets by liquid chromatography isotope dilution mass spectrometry

There is increased interest in accurately assessing the total dietary intake of vitamins from all sources, including foods and dietary supplements. Consequently, a Dietary Supplement Ingredient Database (DSID), based upon analytical values, is being established by USDA with support of the Office of Dietary Supplements (ODS), NIH. The DSID necessitated the development of a new SRM, 3280 — Multivitamin/Multimineral Tablets, by the National Institute of Standards and Technology (NIST), with support from the ODS. As a continuation of a long-term project to develop and validate new methods of determining water-soluble B vitamins in foods and dietary supplements, and as part of a collaborative effort with NIST to characterize SRM 3280, values for the vitamin contents of SRM 3280 have been generated by a liquid chromatographic isotope dilution mass spectrometric (LC/IDMS) method. Isotope-labeled (¹³C and/or ²H) B vitamins (B1-thiamine, B6-pyridoxine, B3-nicotinamide, and B5-pantothenic acid) were obtained from commercial sources, with the support of the ODS/NIH. Our LC/IDMS method uses a C18 reversed phase column, an Agilent 1100 HPLC system, and a Quattro Micro triple-quad mass spectrometer (MS). B vitamin determination was achieved using a gradient LC profile combined with MS/MS detection in multiple reaction monitoring mode. Stock solutions of the isotope-labeled vitamins were calibrated against USP standard solutions. The SRM tablets, with added amounts of the four isotope-labeled B vitamins, were extracted and the vitamins simultaneously determined in a single LC run, in contrast with the single-component determinations performed via IDMS. Unknown vitamin concentrations were calculated by comparing the ratios of the integrated LC peaks at the different masses of the unlabeled and labeled vitamins.