Molecular emission cavity analysis—a new flame analytical technique: Part V. The determination of some sulphur anions

An investigation of the MECA behaviour of sulphate, sulphite, metabisulphite, peroxodisulphate, thiocyanate, thiosulphate and sulphide ions, has shown that ng amounts of these anions may be determined in samples of a few μl. Metal ion interferences in the determination of sulphate and sulphite are removed by addition of phosphoric acid.     

Analysis of various classes of drugs by capillary supercritical fluid chromatography

Three classes of drugs were screened for analysis feasibility by capillary column supercritical fluid chromatography. These included steroids, therapeutic antibiotic drugs, and drugs of abuse, such as cannabinoids. Supercritical fluid carbon dioxide was used as the mobile phase in conjunction with a methylpolysiloxane stationary phase capillary column and a flame ionization detector. All compounds considered were analyzed either as single component solutions, simple mixtures, or in actual complex mixtures.     

Phenomena Affecting the Equilibrium of Al(III) and Zn(II) Extraction with Winsor II Microemulsions

The extraction of Al(III) and Zn(II) from an aqueous solution with two water-in-oil microemulsions, one containing di(2-ethylhexyl)phosphoric acid (DEHPA), was investigated to aid the understanding of the role of the extractant and the metal specific characteristics in the mechanism of microemulsion extraction. The extraction of Al with the DEHPA microemulsion increased by a factor of about 10 with respect to that in the conventional DEHPA system, whereas the extraction of Zn was lower than that in the single DEHPA system. Extraction with the DEHPA-free microemulsion was very low, showing that metal ion solubilization was not important in the mechanism of microemulsion extraction. It is proposed that the effect of the mixed microemulsion on the metal distribution coefficient is the result of the balance between a decrease in the complexation reaction yield due to the interaction between butanol and DEHPA, and the adsorption of the metal complex at the macro- and microinterfaces. The former leads to a decrease in Zn(II) extraction and the latter to Al(III) extraction synergism. Copyright 2000 Academic Press.     

Oxidation of guanosine derivatives by a platinum(IV) complex: internal electron transfer through cyclization

Many transition-metal complexes mediate DNA oxidation in the presence of oxidizing radiation, photosensitizers, or oxidants. The DNA oxidation products depend on the nature of the metal complex and the structure of the DNA. Earlier we reported trans-d,l-1,2-diaminocyclohexanetetrachloroplatinum (trans-Pt(d,l)(1,2-(NH(2))(2)C(6)H(10))Cl(4), [Pt(IV)Cl(4)(dach)]; dach = diaminocyclohexane) oxidizes 2'-deoxyguanosine 5'-monophosphate (5'-dGMP) to 7,8-dihydro-8-oxo-2'-deoxyguanosine 5'-monophosphate (8-oxo-5'-dGMP) stoichiometrically. In this paper we report that [Pt(IV)Cl(4)(dach)] also oxidizes 2'-deoxyguanosine 3'-monophosphate (3'-dGMP) stoichiometrically. The final oxidation product is not 8-oxo-3'-dGMP, but cyclic (5'-O-C8)-3'-dGMP. The reaction was studied by high-performance liquid chromatography, (1)H and (31)P nuclear magnetic resonance, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. The proposed mechanism involves Pt(IV) binding to N7 of 3'-dGMP followed by nucleophilic attack of a 5'-hydroxyl oxygen to C8 of G and an inner-sphere, 2e(-) transfer to produce cyclic (5'-O-C8)-3'-dGMP and [Pt(II)Cl(2)(dach)]. The same mechanism applies to 5'-d[GTTTT]-3', where the 5'-dG is oxidized to cyclic (5'-O-C8)-dG. The Pt(IV) complex binds to N7 of guanine in cGMP, 9-Mxan, 5'-d[TTGTT]-3', and 5'-d[TTTTG]-3', but no subsequent transfer of electrons occurs in these. The results indicate that a good nucleophilic group at the 5' position is required for the redox reaction between guanosine and the Pt(IV) complex.     

Structural analysis of phosphatidylcholines by post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The utility of post-source decay (PSD) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was investigated for the structural analysis of phosphatidylcholine (PC). PC did not produce detectable negative molecular ion from MALDI, but positive ions were observed as both [PC+H](+) and [PC+Na](+). The PSD spectra of the protonated PC species contained only one fragment corresponding to the head group (m/z 184), while the sodiated precursors produced many fragment ions, including those derived from the loss of fatty acids. The loss of fatty acid from the C-1 position (sn-1) of the glycerol backbone was favored over the loss of fatty acid from the C-2 position (sn-2). Ions emanating from the fragmentation of the head group (phosphocholine) included [PC+Na-59](+), [PC+Na-183](+) and [PC+Na-205](+), which corresponded to the loss of trimethylamine (TMA), non-sodiated choline phosphate and sodiated choline phosphate, respectively. Other fragments reflecting the structure of the head group were observed at m/z 183, 146 and 86. The difference in the fragmentation patterns for the PSD of [PC+Na](+) compared to [PC+H](+) is attributed to difference in the binding of Na(+) and H(+). While the proton binds to a negatively charged oxygen of the phosphate group, the sodium ion can be associated with several regions of the PC molecule. Hence, in the sodiated PC, intermolecular interaction of the negatively charged oxygen of the phosphate group, along with sodium association at multiple sites, can lead to a complex and characteristic ion fragmentation pattern. The preferential loss of sn-1 fatty acid group could be explained by the formation of an energetically favorable six-member ring intermediate, as apposed to the five-member ring intermediate formed prior to the loss of sn-2 fatty acid group.     

Electronic transport in graphene nanostructures on SiO2

We report two experiments on graphene nanostructures. The first was performed on a graphene nanoribbon, where the nature of electronic transport was investigated in detail. Electrons or holes are found to localize in pockets of the potential along the ribbon. Transport is governed by the joint action of localization and Coulomb interaction. The temperature-dependence of the conductance shows activated behavior at temperatures above a few Kelvin. The activation energy retraces the edges of Coulomb blockade diamonds found in nonlinear transport. In the second experiment the metallic tip of a low-temperature scanning force microscope was scanned above a graphene quantum dot. In addition to the familiar Coulomb blockade fringes, localized states are detected forming in the constrictions connecting the dot to source and drain.     

Batch versus Flow Photochemistry: A Revealing Comparison of Yield and Productivity

The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20 % lower than that of batch, whereas three‐layer reactors were 20 % more productive. Finally, the utility of flow chemistry was demonstrated in the scale‐up of the ring‐opening reaction of a potentially explosive [1.1.1] propellane with butane‐2,3‐dione.