Untersuchung von Honig und Kunsthonig

Ohne Zusammenfassung     

The S.M.A.R.T. (small mass,affordable, rapid,transfer-less) digestion method for heavy metal determinations

The S.M.A.R.T. (small mass, affordable, rapid, transfer-less) digestion method was developed to determine heavy metal concentrations in small sample masses. The S.M.A.R.T. digestion method is a hot water bath digestion where sample digestion and dilution are performed in the original sample tube. This method is faster than the typical methods used and reduces potential sources of error. Masses as small as 0.01 g have been digested and analysed using this method. The preparation and digestion time is reduced from 10 h to less than 4 h. Acid volumes are reduced from millilitres to microlitres and the only disposable supplies needed are sample tubes and pipette tips. Method accuracy was determined by digesting seven replicates of two standard reference materials using the S.M.A.R.T. method and analysing samples by inductively coupled plasma mass spectrometry. The S.M.A.R.T. digestion method was found to provide excellent recoveries for Al (76 ± 2.7%), Mn (99 ± 11%), Co (92 ± 17%), Ni (93 ± 28%), Cu (109 ± 33%), Zn (97 ± 7.1%), As (108 ± 20%), Sr (90 ± 12%), Mo (84 ± 23%), Ag (91 ± 1.8%), Cd (95 ± 6.2%), Sn (139 ± 52%) and Pb (95 ± 22%). This study has successfully developed an efficient and reproducible digestion method for heavy metal determination in limited biomass samples.     

The artificial binaphthyl amino acid 6-amino-6′-carboxyethyl-2-methoxy-2′-hydroxy-1,1′-binaphthyl (Bna): synthesis and assembly of Bna peptides

The new binaphthyl-based amino acid 6-amino-6′-carboxyethyl-2-methoxy-2′-hydroxy-1,1′-binaphthyl (Bna) is presented, which combines the axially chiral binaphthyl core, a phenolic OH-group as well as terminating amino and carboxyl groups in one structure. The large aromatic rings of the compound provide molecular spacing and π-surface attraction in assembled Bna oligoamides. The synthesis of Bna derivatives is reported, both with the (R)- and with the (S)-binaphthyl skeleton. Several dipeptides of (R)- or (S)-Bna units combined with natural amino acids, were prepared as ‘building blocks’ for the synthesis of extended Bna peptides. The tetrapeptide Boc-(S)-Val-(S)-Bna(OH)-(S)-Val-(S)-Bna(OPiv)-O-n-But (12) and the pentapeptide Boc-(S)-Val-(S)-Bna(OH)-(S)-Val-(S)-Bna(OH)-Gly-OH (13) were prepared via conventional solution phase synthesis and solid phase synthetic techniques, respectively. Compound 12 shows an interesting dynamic ¹H NMR spectrum suggesting compact and aggregated forms in dichloromethane. Compound 13 accelerates the enolisation of acetone. The use of more complex Bna peptides as organo catalysts is proposed.     

Water-soluble organo-silica hybrid nanotubes templated by cylindrical polymer brushes

We report the preparation of water-soluble organo-silica hybrid nanotubes templated by core-shell-corona structured triblock terpolymer cylindrical polymer brushes (CPBs). The CPBs consist of a polymethacrylate backbone, a poly(tert-butyl acrylate) (PtBA) core, a poly(3-(trimethoxysilyl)propyl acrylate) (PAPTS) shell, and a poly(oligo(ethylene glycol) methacrylate) (POEGMA) corona. They were prepared via the "grafting from" strategy by the combination of two living/controlled polymerization techniques: anionic polymerization for the backbone and atom transfer radical polymerization (ATRP) for the triblock terpolymer side chains. The monomers tBA, APTS, and OEGMA were consecutively grown from the pendant ATRP initiating groups along the backbone to spatially organize the silica precursor, the trimethoxysilyl groups, into a tubular manner. The synthesized core-shell-corona structured CPBs then served as a unimolecular cylindrical template for the in situ fabrication of water-soluble organo-silica hybrid nanotubes via base-catalyzed condensation of the PAPTS shell block. The formed tubular nanostructures were characterized by transmission electron microscopy (TEM), cryogenic TEM, and atomic force microscopy.     

Binary boron-rich borides of magnesium: single-crystal investigations and properties of MgB(7) and the new boride Mg(∼5)B(44)

Single crystals of dark-red MgB(7) were grown from the elements in a Cu-melt. The crystal structure (Pearson symbol oI64; space group Imma; a = 10.478(2) ?, b = 5.977(1) ?, c = 8.125(2) ?, 2842 reflns, 48 params, R(1)(F) = 0.018, R(2)(I) = 0.034) consists of a hexagonal-primitive packing of B(12)-icosahedra and B(2)-units in trigonal-prismatic voids. According to the UV-vis spectra and band structure calculations MgB(7) is semiconducting with an optical gap of 1.9 eV. The long B-B distance of 2.278 ? within the B(2)-unit can be seen as a weak bonding interaction. The new Mg(～5)B(44) occurs beside the well-known MgB(12) as a byproduct. Small fragments of the black crystals are dark-yellow and transparent. The crystal structure (Pearson symbol tP196, space group P4(1)2(1)2, a = 10.380(2) ?, c = 14.391(3) ?, 4080 reflns, 251 params, R(1)(F) = 0.025, R(2)(I) = 0.037) is closely related to tetragonal boron-II (t-B(192)). It consists of B(12)-icosahedra and B(19+1)-units. With a charge of -6 for the B(19+1)-units and a Mg-content of ～20 Mg-atoms per unit cell the observed Mg content in Mg(～5)B(44) is quite close to the expected value derived from simple electron counting rules. All compositions were confirmed by EDXS. The microhardness was measured on single crystals for MgB(7) (H(V) = 2125, H(K) = 2004) and MgB(12) (H(V) = 2360, H(K) = 2459).     

Alignment of retention time obtained from multicapillary column gas chromatography used for VOC analysis with ion mobility spectrometry

Multicapillary column (MCC) ion mobility spectrometers (IMS) are increasingly in demand for medical diagnosis, biological applications and process control. In a MCC-IMS, volatile compounds are differentiated by specific retention time and ion mobility when rapid preseparation techniques are applied, e.g. for the analysis of complex and humid samples. Therefore, high accuracy in the determination of both parameters is required for reliable identification of the signals. The retention time in the MCC is the subject of the present investigation because, for such columns, small deviations in temperature and flow velocity may cause significant changes in retention time. Therefore, a universal correction procedure would be a helpful tool to increase the accuracy of the data obtained from a gas-chromatographic preseparation. Although the effect of the carrier gas flow velocity and temperature on retention time is not linear, it could be demonstrated that a linear alignment can compensate for the changes in retention time due to common minor deviations of both the carrier gas flow velocity and the column temperature around the MCC-IMS standard operation conditions. Therefore, an effective linear alignment procedure for the correction of those deviations has been developed from the analyses of defined gas mixtures under various experimental conditions. This procedure was then applied to data sets generated from real breath analyses obtained in clinical studies using different instruments at different measuring sites for validation. The variation in the retention time of known signals, especially for compounds with higher retention times, was significantly improved. The alignment of the retention time—an indispensable procedure to achieve a more precise identification of analytes—using the proposed method reduces the random error caused by small accidental deviations in column temperature and flow velocity significantly.     

Tetramethylcyclopentadienyl-supported rare-earth metal bis(tetramethyl)aluminate complexes: Synthesis,structural chemistry,cation formation,and isoprene polymerization

The protonolysis reaction of [Ln(AlMe₄)₃] with H(Cp′) (Cp′ = C₅Me₄H) gives access to half-sandwich complexes [(Cp′)Ln(AlMe₄)₂]. X-ray structure analyses of the samarium, neodymium, and lanthanum derivatives reveal a distinct [AlMe₄] coordination (one η², one bent η²) for the two smaller rare-earth metals. The lanthanum complex displays an unprecedented dimeric structure with two μ₂-η¹:η² coordinating [AlMe₄] ligands in the solid state. Treatment of complexes [(Cp′)Ln(AlMe₄)₂] with perfluorinated organoborates and -boranes produces discrete contact ion-pairs, which are characterized by ¹H, ¹³C, ²⁷Al, ¹⁹F, and ¹¹B NMR spectroscopy and act as efficient initiators for the fabrication of trans-1,4 polyisoprene. The polymerization performance is hereby affected by the rare-earth metal cation size, the type of boron cocatalyst, and the polymerization temperature.     

Simultaneous analysis of 70 pesticides using HPlc/MS/MS: a comparison of the multiresidue method of Klein and Alder and the QuEChERS method

Since 2003, two new multipesticide residue methods for screening crops for a large number of pesticides, developed by Klein and Alder and Anastassiades et al. (Quick, Easy, Cheap, Effective, Rugged, and Safe; QuEChERS), have been published. Our intention was to compare these two important methods on the basis of their extraction efficiency, reproducibility, ruggedness, ease of use, and speed. In total, 70 pesticides belonging to numerous different substance classes were analyzed at two concentration levels by applying both methods, using five different representative matrixes. In the case of the QuEChERS method, the results of the three sample preparation steps (crude extract, extract after SPE, and extract after SPE and acidification) were compared with each other and with the results obtained with the Klein and Alder method. The extraction efficiencies of the QuEChERS method were far higher, and the sample preparation was much quicker when the last two steps were omitted. In most cases, the extraction efficiencies after the first step were approximately 100%. With extraction efficiencies of mostly less than 70%, the Klein and Alder method did not compare favorably. Some analytes caused problems during evaluation, mostly due to matrix influences.