Chromatographic separation of diastereoisomeric esters-II Mandelates and lactates of 2-methylbutanol-1, 3-methylbutanol-2, pentanol-2 and hexanol-2

The racemic alcohols, 2-methylbutanol-l, 3-methylbutanol-2, pentanol-2 and hexanol-2 have been esterified with optically active mandelic or lactic acid, and the resultant mixtures of diastereoisomeric esters separated chromatographically with an optically inactive sulphonated polystyrene resin as the stationary phase and water or dilute aqueous sodium sulphate as the mobile phase. Lactate esters were more easily separated than mandelate esters. The Chromatographic separation of 26 mmole of (+/-)-3-methyl-2-butyl(+)-lactate and subsequent hydrolysis of the fractions containing only the ester of the (+)-alcohol yielded 1-2 mmole of pure 3-methyl-2-butanol.     

Development of the time course for processing conflict: an event-related potentials study with 4 year olds and adults

Background

The neurological complications of HIV infection remain poorly understood. Clinically, in vivo ¹H magnetic resonance spectroscopy (MRS) demonstrates brain injury caused by HIV infection even when the MRI is normal. Our goal was to undertsand the dynamics of cerebral injury by performing a longitudinal in vivo ¹H MRS study of the SIV/macaque model of neuroAIDS.

Results

Eight rhesus macaques were infected with SIVmac251 and serially imaged with MRI and ¹H MRS to terminal AIDS or the endpoint of 2 years. During acute infection, there were stereotypical brain MRS changes, dominated by a significant elevation of the Cho/Cr ratio in the frontal cortex. Subsequently, brain metabolic patterns diverged between animals. There was an elevation of basal ganglia Cho/Cr four weeks post-inoculation in 2 animals that developed SIV encephalitis (p = 0.022). Metabolite ratios averaged across all 8 animals were not significantly different from baseline at any time point after 2 weeks post inoculation. However, linear regression analysis on all 8 animals revealed a positive correlation between a change in frontal lobe Cho/Cr and plasma viral load (P < 0.001, R = 0.80), and a negative correlation between NAA/Cr in the basal ganglia and the plasma viral load (P < 0.02, R = -0.73). No MRI abnormalities were detected at any time.

Conclusions

After infection with SIV, macaque brain metabolism changes in a complex manner that is dependent on brain region, host factors and viral load. An elevation of basal ganglia Cho/Cr 4 weeks after SIV infection may be marker of a propensity to develop SIV encephalitis. Elevations of Cho/Cr, often observed in CNS inflammation, were associated with increased plasma viral load during acute and chronic infection. Evidence of neuronal injury in the basal ganglia was associated with increased plasma viral load in the chronic stage of infection. These observations support the use of drugs capable of controlling the viral replication and trafficking of virus into the CNS, and may help explain the reduction in incidence of HIV-associated dementia in the era of HAART despite the inability of most of those drugs to effectively enter the CNS.     

Development of the time course for processing conflict: an event-related potentials study with 4 year olds and adults

Background  

Tasks involving conflict are widely used to study executive attention. In the flanker task, a target stimulus is surrounded by distracting information that can be congruent or incongruent with the correct response. Developmental differences in the time course of brain activations involved in conflict processing were examined for 22 four year old children and 18 adults. Subjects performed a child-friendly flanker task while their brain activity was registered using a high-density electroencephalography system.     

Resolution of racemic substances by liquid ion-exchange

Two optically active liquid anion-exchangers have been synthesized. The separation factors of the enantiomers of sodium (+/-)-mandelate and sodium-N-acetyl-(+/-)-alanate have been determined by batchwise equilibration of aqueous solutions of the salts with chloroform solutions of each of the exchangers. Sodium mandelate has been resolved by Craig countercurrent extraction with one of these exchangers. Optically pure products can be obtained even though the liquid ion-exchanger is not optically pure.     

On the Relationship Between Instrument and Specimen in Chemical Research

Based on the design of many modern chemical instruments, information about a specimen is retrieved after the specimen undergoes agitation, manipulation and disturbance of its internal state. But can we retain the traditional ideal that instruments should reveal properties that are definable independently of all modes of detection? In this paper I argue that the capacity of chemical instruments to convert experimental phenomena to information places constraints on the way in which the specimen is characterized. During research, the specimen is defined by those properties which permit its detection. Based on modern instrumentation, this constraint necessitates a conception of the specimen as a reactive system of dynamical properties. The dream of a purely transparent detection process violates the design of chemical instruments. This mutual dependence of instrument and specimen is illustrated by empirical studies of the geometrical configuration of DNA.     

Observations on the rapid size-exclusion chromatography of proteins

Summary The retention behaviour of reference proteins on commercial siliceous size-exclusion supports was studied. Sorption was observed on both surface modified and unmodified supports. When sodium dodecylsulfate was added to the aqueous mobile phase, normal elution patterns were found. With this system, proteins, such as those isolate from different alfalfa genotypes, may be compared rapidly. Comparisons were facillitated by use of on-line central data processing capability.     

Toward a physical basis of attention and self-regulation

The concept of self-regulation is central to the understanding of human development. Self-regulation allows effective socialization and predicts both psychological pathologies and levels of achievement in schools. What has been missing are neural mechanisms to provide understanding of the cellular and molecular basis for self-regulation. We show that self-regulation can be measured during childhood by parental reports and by self-reports of adolescents and adults. These reports are summarized by a higher order factor called effortful control, which reflects perceptions about the ability of a given person to regulate their behavior in accord with cultural norms. Throughout childhood effortful control is related to children's performance in computerized conflict related tasks. Conflict tasks have been shown in neuroimaging studies to activate specific brain networks of executive attention. Several brain areas work together at rest and during cognitive tasks to regulate competing brain activity and thus control resulting behavior. The cellular structure of the anterior cingulate and insula contain cells, unique to humans and higher primates that provide strong links to remote brain areas. During conflict tasks, anterior cingulate activity is correlated with activity in remote sensory and emotional systems, depending upon the information selected for the task. During adolescence the structure and activity of the anterior cingulate has been found to be correlated with self-reports of effortful control.Studies have provided a perspective on how genes and environment act to shape the executive attention network, providing a physical basis for self-regulation. The anterior cingulate is regulated by dopamine. Genes that influence dopamine levels in the CNS have been shown to influence the efficiency of self-regulation. For example, alleles of the COMT gene that influence the efficiency of dopamine transmission are related to the ability to resolve conflict. Humans with disorders involving deletion of this gene exhibit large deficits in self-regulation. Alleles of other genes influencing dopamine and serotonin transmission have also been found to influence ability to resolve conflict in cognitive tasks. However, as is the case for many genes, the effectiveness of COMT alleles in shaping self-regulation depends upon cultural influences such as parenting. Studies find that aspects of parenting quality and parent training can influence child behavior and the efficiency of self-regulation.During development, the network that relates to self-regulation undergoes important changes in connectivity. Infants can use parts of the self-regulatory network to detect errors in sensory information, but the network does not yet have sufficient connectivity to organize brain activity in a coherent way. During middle childhood, along with increased projection cells involved in remote connections of dorsal anterior cingulate and prefrontal and parietal cortex, executive network connectivity increases and shifts from predominantly short to longer range connections. During this period specific exercises can influence network development and improve self-regulation. Understanding the physical basis of self-regulation has already cast light on individual differences in normal and pathological states and gives promise of allowing the design of methods to improve aspects of human development.