In situ scanning tunneling microscopy: New insight for electrochemical electrode-surface investigations

The successful expansion which the scanning tunneling microscopy (STM) has had is dependent on its ability to examine surfaces on a sub-nanometric scale and on providing in situ (i.e. in the presence of bulk electrolyte) sample examination. In addition to the ability to study metals and semiconductors in vacuo, the application of the technique to surfaces in contact with an electrolytic solution has prompted increased interest amongst electrochemists. We discuss herein the technique, with particular reference to advances in electrochemical applications. A new scanning tunneling microscope for operation in electrolytic environments is described. Atomic force microscopy, scanning electrochemical microscopy and scanning ion-conducting microscopy are compared with the STM.     

Thermolytic behavior of polydienyllithium and polystyryllithium

UV absorption spectra of thermolyzed polybutadienyl- and polyisoprenyl-lithium reveal a chromophore group previously not recognized for such systems; its absorption band at 271 nm has been assigned to a structure with three conjugated double bonds. A two-step mechanism for the formation of this trienic structure is proposed: an intermolecular metallation of associated living ends is followed by lithium hydride (LiH) elimination. Along thermolysis the presence of a dienic structure was also recognized, the latter arising from intramolecular elimination of LiH. The trienyllithium structure is also considered to be an effective species for the observed molecular weight distribution (MWD) variations. The observed different extent of high molecular weight (HMW) for polyisoprenyl- and polybutadienyl-lithium is explained on the basis of a different stability of the intermediates present along the proposed reaction mechanism. The thermolytic behavior of polystyryllithium does not provide any significant change in MWD: the disappearance of the living chain ends, UV detected, is due to an intramolecular LiH elimination which obeys first-order kinetics. The influence of temperature and of the tetrahydrofuran (THF) level on kinetic rate constants was investigated. © 1996 John Wiley & Sons, Inc.     

Evidence for the intermediacy of Wheland-Meisenheimer complexes in SEAr reactions of aminothiazoles with 4,6-dinitrobenzofuroxan

Reactions of DNBF with a series of 2-aminothiazoles (1 a-f) to afford thermodynamically stable C-bonded sigma-adducts have been investigated in acetonitrile. A most significant finding emerged on recording NMR spectra immediately after mixing of equimolar amounts of DNBF and the unsubstituted 2-aminothiazole (1 a) in Me2SO: namely, that the formation of 9 a is preceded by that of a short-lived intermediate species X. From the 1H NMR parameters characterizing this intermediate, as well as the dependence of its lifetime on the experimental conditions-the presence of excess DNBF over 1 a increases the lifetime of X while an excess of base (1 a) accelerates its conversion into 9 a--it is convincingly demonstrated that the structure of X combines the presence of a positively charged Wheland complex moiety (with regard to the thiazole ring) with that of a negatively charged Meisenheimer complex moiety (with regard to the benzofuroxan system). So far, only one intermediate of this type (noted WM) has been successfully characterized, in the reactions of DNBF with 1,3,5-tris(N,N-dialkylamino)benzenes. Among the key features supporting the intermediacy of X along the reaction coordinate leading to 9 a is the fact that the reactions of DNBF with 1 a in the presence of an alcohol (MeOH, EtOH, nPrOH) produce new adducts arising from the addition of an alcohol molecule to the thiazole moiety of WM-1 a. Reflecting the presence of three chiral centres, these species are formed as mixtures of several diastereomers that could all be characterized in their racemic forms in ethanol. These findings generalize the previous report on the formation of Wheland-Meisenheimer carbon-carbon complexes in homocyclic series.     

Easy DNA extraction for rapid detection of Panax ginseng C. A. Meyer in commercial ginseng products

An investigation was carried out in order to obtain an easy and rapid detection of Panax ginseng in commercial herbal products by using molecular techniques (polymerase chain reaction (PCR) and restriction fragment length polymorphism (RFLP)). Two protocols and one commercial kit for DNA extraction were used. Four forms of commercial products were considered, i.e., dried body roots, dried root tails, dried root prongs and dried extracts. The RFLP of DNA amplified products by 18df/28ccr primers, obtained using Inf I, Sau 3A1 and Taq I endonucleases, allowed the identification of P. ginseng and its differentiation from P. quinquefolium. The presence of adulterants, as Mirabilis jalapa L. and Phytolacca acinosa Roxb. was excluded in the examined commercial samples. P. ginseng was detected in 63% of the considered samples according to the declaration of the labels, whereas negative results were obtained with the dried extract form. Therefore, the Invitrogen DNA extraction kit let the easy extraction of useful amounts of DNA and a standardisation of routine work, in comparison with the other molecular protocols so far used.     

Large-volume sample stacking for the analysis of seven beta-lactam antibiotics in milk samples of different origins by CZE

A method for the simultaneous determination of eight beta-lactam antibiotics (nafcillin, cloxacillin, oxacillin, dicloxacillin, ampicillin, amoxicillin, and penicillin G) in fortified milk samples of different origins has been proposed by using CZE with diode-array detection (CZE-DAD). Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using 175 mM Tris buffer with 20% ethanol at pH 8.0. Methylparaben has been used as an internal standard (IS). Taking into account the lack of sensitivity of the UV-Vis detection, a solvent extraction/SPE method was applied for off-line preconcentration and sample cleanup, and also an on-line preconcentration methodology, such as large-volume sample stacking (LVSS) with polarity switching, was developed, providing LODs ranging from 2 to 10 microg/L. The method permits the quantification of these residues below the levels established in milk by the EU Regulation. Satisfactory recoveries ranging from 86 to 93% were also obtained in milk samples of different origins.     

Selenium speciation in foods: Preliminary results on potatoes

The present paper deals with the speciation of selenium in potatoes (enriched or not in selenium). The study was carried out by using differential pulse cathodic stripping voltammetry (DPCSV) for quantifying selenium. Results obtained provide evidence that the selenium content in the protein fraction is rather independent from the selenium added to the plants during their growth. On the contrary, the amount of Se in the non-protein fraction (water and starch) in Se-enriched sample is significantly higher than in non-enriched one, suggesting that it is the main selenium-storing site. In this fraction the Se(VI)/Se(IV) ratio seems independent from selenium application but it may be related to the redox conditions. The accumulation of selenium in the non-protein fraction is tentatively ascribed to the “Se–starch interaction” that should be able to modulate both the Se absorption into proteins and, possibly, its toxic effect for the plant itself.     

Theoretical study on Pd dimer and trimer interaction with the hydrogen molecule

The H₂ interaction with the Pd dimer and trimer were studied using multiconfigurational self-consistent field (MC-SCF) calculations with the relativistic effective core potential (RECP); the correlation energy correction was included in the extended multireference configuration interaction (MRCI), variational and perturbative to second order. Here, we considered the Pd₂ first six states: ³Σ⁺_u, ¹Σ⁺_g, ³Π_g, ³Δ_xy, ¹Σ⁺_u, and ³Σ⁺_g. For them, the four geometrical approaches included were the side-on H₂ toward Pd₂, for the hydrogen molecule in and out the Pd dimer plane; the perpendicular end-on H₂ toward Pd₂; and the perpendicular end-on Pd₂ to H₂. The Pd₂ ground state is ³Σ⁺_u, which only captures H₂ in the C_2v end-on approach, softly relaxing the H(SINGLE BOND)H bond. The closed-shell ¹Σ⁺_g captures the H₂ molecule in all the approaches considered: The side-on approach of this state presents deep wells and relaxes the H(SINGLE BOND)H bond, and the end-on approach captures H₂ with a relatively longer H(SINGLE BOND)H distance and also a deep well. The ³Π_g state was the only one which did not capture H₂. For the triangular Pd₃ clusters, H₂ was approached in the C_2v symmetry in and out of the Pd₃ plane. In the triangular case, H₂ was absorbed in both spin states, with deep wells and relaxing the H(SINGLE BOND)H distance. The linear Pd₃ singlet and triplet states capture outside of the Pd₃ and break the H(SINGLE BOND)H bond. © 1997 John Wiley & Sons, Inc.     

Isopropenyl acetate: A cheap and general acylating agent of alcohols under metal-free conditions

Functionalized primary, secondary and tertiary alcohols are efficiently acetylated by isopropenyl acetate and catalytic p-TsOH.     

New Features in the Lipid A Structure of <Emphasis Type="Italic">Brucella suis</Emphasis> and <Emphasis Type="Italic">Brucella abortus</Emphasis> Lipopolysaccharide

Brucellaceae are Gram-negative bacteria that cause brucellosis, one of the most distributed worldwide zoonosis, transmitted to humans by contact with either infected animals or their products. The lipopolysaccharide exposed on the cell surface has been intensively studied and is considered a major virulence factor of Brucella. In the last years, structural studies allowed the determination of new structures in the core oligosaccharide and the O-antigen of this lipopolysaccharide. In this work, we have reinvestigated the lipid A structure isolated from B. suis and B. abortus lipopolysaccharides. A detailed study by MALDI-TOF mass spectrometry in the positive and negative ion modes of the lipid A moieties purified from both species was performed. Interestingly, a new feature was detected: the presence of a pyrophosphorylethanolamine residue substituting the backbone. LID-MS/MS analysis of some of the detected ions allowed assurance that the Lipid A structure composed by the diGlcN3N disaccharide, mainly hexa-acylated and penta-acylated, bearing one phosphate and one pyrophosphorylethanolamine residue.

Open image in new window

Graphical abstract ?