Sequential photooxidation of a Pt(II) (diimine)cysteamine complex: intermolecular oxygen atom transfer versus sulfinate formation.

The thiolato complex [platinum(II) (bipyridine)(N,S-aminoethanethiolate)](+)Ch(-) (1) undergoes sequential reactions with singlet oxygen to initially form the corresponding sulfenato complex [platinum(II) (bipyridine)(N,S(═O)-aminoethansulfenate)](+) (2) followed by a much slower reaction to the corresponding sulfinato complex. In contrast with many platinum dithiolato complexes, 1 does not produce any singlet oxygen, but its rate constant for singlet oxygen removal (k(T)) is quite large (3.2 × 10(7) M(-1) s(-1)) and chemical reaction accounts for ca. 25% of the value of k(T). The behavior of 1 is strikingly different from that of the complex platinum(II) (bipyridine)(1,2-benzenditholate) (4). The latter complex reacts with (1)O(2) (either from an external sensitizer or via a self-sensitized pathway) to form a sulfinato complex. These two very different reactivity pathways imply different mechanistic pathways: The reaction of 1 with (1)O(2) must involve O-O bond cleavage and intermolecular oxygen atom transfer, while the reactive intermediate in complex 4 collapses intramolecularly to the sulfinato moiety.

Electroencephalography to assess motor control during balance tasks in people with diabetes.

BACKGROUND: Balance is sensed through peripheral and central receptors and mediated by central control through the brain and spinal cord. Although some evidence exists as to the areas of the brain involved and how processing of data occurs in young individuals, nothing has been published on people with diabetes. The purpose of this study was to examine the electroencephalogram (EEG) during common sensorimotor and balance training tasks and to relate these to task difficulty. SUBJECTS AND METHODS: Postural sway and EEG change of alpha, beta, and sigma wave bands were measured in 17 young subjects, 10 older subjects, and 10 subjects with diabetes during eight progressively more difficult balance tasks with eyes open and closed, feet in tandem or apart, and on foam or a firm surface. RESULTS: EEG power of beta and sigma wave bands showed significant increases on the cortical and parietal areas of the brain relative to the control tasks when eyes were open (P<0.05). The cortical involvement decreased as the task became more difficult with vision and somatosensory information reduced, whereas that of the parietal area increased with task difficulty. The greatest increase was in subjects with diabetes, and the least was in younger people. Individuals with diabetes had increased sigma and beta EEG power in all regions of the brain examined with increased complexity of the balance task. CONCLUSIONS: This study demonstrated cortical and parietal involvement in static balance tasks commonly used in sensorimotor training. The results support the proposal that there was increased subcortical control with increase in task difficulty in the young subjects, but in subjects with diabetes, there was a major increase in activity across the brain.

Design and development of a flow injection-capillary electrophoresis analyzer employing fiber optic detection.

The development and experimental optimization of a novel flow injection-capillary electrophoresis (FI-CE) analyzer employing UV-visible fiber optic detection is described. The analyzer incorporates a miniature charge-coupled device (CCD) spectrometer and operates in a graphical programming environment. Data from experimental optimization studies and small molecule separations involving affinity capillary electrophoresis (ACE) and indirect detection of anions are presented. Future directions in terms of instrument automation and incorporation into a microfluidic format are also discussed.