General approach for the stereocontrolled construction of the beta-lactam ring in amino acid-derived 4-alkyl-4-carboxy-2-azetidinones

The first general approach toward the asymmetric synthesis of 4-alkyl-4-carboxy-2-azetidinones derived from amino acids is described. The stereoselective construction of the beta-lactam ring was achieved through base-mediated intramolecular cyclization of the corresponding N(alpha)-chloroacetyl derivatives bearing (+)- or (-)-10-(N,N-dicyclohexylsulfamoyl)isoborneol as chiral auxiliary (ee up to 82%).     

Polarity switching and transient responses in single nanotube nanofluidic transistors

We report the integration of inorganic nanotubes into metal-oxide-solution field effect transistors (FETs) which exhibit rapid field effect modulation of ionic conductance. Surface functionalization, analogous to doping in semiconductors, can switch the nanofluidic transistors from p-type to ambipolar and n-type field effect transistors. Transient study reveals the kinetics of field effect modulation is controlled by ion-exchange step. Nanofluidic FETs have potential implications in subfemtoliter analytical technology and large-scale nanofluidic integration.     

Pairing fluctuations in trapped fermi gases

We examine the contribution of pairing fluctuations to the superfluid order parameter for harmonically trapped atomic Fermi gases in the BCS regime. In the limit of small systems we consider, both analytically and numerically, their space and temperature dependence. We predict a parity effect, i.e., that pairing fluctuations show a maximum or a minimum at the center of the trap, depending on the value of the last occupied shell being even or odd. We propose to detect pairing fluctuations by measuring the density-density correlation function after a ballistic expansion of the gas.     

Masked omega-lithio ester enolates: synthetic applications

The protocol of lithiation by means of lithium and a catalytic (5% molar) amount of DTBB (4,4'-di-tert-butylbiphenyl), applied to omega-chloro ortho ester 6 under Barbier-type conditions gives, after final acid-catalyzed methanolysis, the corresponding functionalized esters 8 or 9 (for chlorotrimethylsilane as electrophile) or, after ortho ester deprotection and acid catalyzed treatment, the delta-lactones 11. The procedure is also practical for bicyclic ortho esters 14: the beta-chloro OBO ester derivate generates the gamma- lactones 15 and the gamma-chloro OBO ester gives corresponding esters 8.     

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.     

Richness of isomerism in labile octahedral Werner-type cobalt(II) complexes demonstrated by 19F NMR spectroscopy: structure and stability

The cobalt(II) complexes [CoL2(R2-Py)2] (1-4) where HLA = 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, R2-Py = 4-methylpyridine (1), HLB = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione, R2-Py = 4-methylpyridine (2), 4-phenylpyridine (3) and S-(-)-1-(4-pyridyl)ethanol (4) were prepared by two-step reactions. X-ray structure analysis of [CoLA2(CH3-Py)2] revealed the {trans(N)-trans(CF3)-trans} configuration for the complex obtained by crystallization from ethanol. A dynamic equilibrium between the five possible stereoisomers was observed for each complex 1-4 in solution by 19F NMR spectroscopy. The criteria used for full NMR assignment (180-265 K) include comparison of integral ratios, cis(N) and trans(N) differentiation in presence of the chiral amine [S-(-)-1-(4-pyridyl)ethanol], effect of solvent polarity on the relative stabilities of the five isomers and observation of trans influences in a mixture of complexes. Thermodynamic parameters for the equilibria between the isomers of 2 in CD2Cl2 (DeltaHi,j, DeltaSi,j and Ki,j) were obtained from signal integrals. The two trans(N) isomers are slightly more stable than the three cis(N) isomers at low temperature [DeltaGdegreesi,j (max) = 2.8 kJ mol(-1) at 179.8 K], but this stability difference almost vanishes with increasing temperature [DeltaGdegreesi,j (max) = 1.0 kJ mol(-1) at 265.0 K]. The values found for DeltaHdegreesi,j are relatively small and largely entropy compensated.