Organic reactions in frozen water: Michael addition of amines and thiols to the dehydroalanine side chain of nocathiacins

Nocathiacins are densely functionalized cyclic thiazolyl peptide natural products with potent in vitro and in vivo antibacterial activity against a variety of gram-positive bacteria, including a number of multiple drug-resistant strains. Attempts to prepare Michael adducts using known conditions resulted in the formation of complex mixture of products. In order to overcome this problem, we developed unique conditions in which Michael addition of amine and thiol nucleophiles to the dehydroalanine moiety of nocathiacins was successfully achieved in frozen water. Under these conditions, the Michael addition was highly chemoselective, very efficient and provided good isolated yields of the desired products.     

Error growth in the numerical integration of periodic orbits by multistep methods, with application to reversible systems

We study the growth with time of (the coefficients of the asymptoticexpansion of) the error in the numerical integration with linearmultistep methods of periodic solutions of systems of ordinarydifferential equations. Particular attention is devoted to reversiblesystems. It turns out that symmetric linear multistep methodscannot be recommended in spite of the fact that they mimic thereversibility of the true flow. For reversible second-ordersystems, linear multistep methods without parasitic double rootsare useful.     

13C NMR spectra of cassane diterpenoids. The stereochemistry of the caesalpins

Assignments of the ¹³C NMR resonances for some cassane diterpenoids have been made. The data have proved to be a useful tool for the stereochemical examination of the caesalpins.     

Measuring the top quark mass in the eµ channel: A study

We describe a simple method to measure the top quark mass in the channel that may be useful in Run II of D? detector. The method is validated by applying it to the Run Ib eμ data.     

Level structures of 95,97Mo — A comparative study

High-spin states of ^95,97Mo (Z=42, N=53,55) nuclei have been investigated through ⁸²Se(¹⁸O, xn) reaction at Eb=60 MeV. The level scheme in ⁹⁵Mo has been observed upto ≏ 10 MeV in the present experiment. The level structure shows mainly single particle character. In ⁹⁷Mo, the ground state level sequence has been extended to ≏ 4.5 MeV while the previous information had been up to 2.4 MeV. A negative parity band built on 1437 keV (11/2⁻) excited state has been extended to 5.5 MeV. The structure seems to show a coexistence of single particle and collective modes of excitation. Properties of both the nuclei have been compared with shell model calculations using OXBASH.     

Development of a universal measure of quadrupedal forelimb-hindlimb coordination using digital motion capture and computerised analysis

Background  

Clinical spinal cord injury in domestic dogs provides a model population in which to test the efficacy of putative therapeutic interventions for human spinal cord injury. To achieve this potential a robust method of functional analysis is required so that statistical comparison of numerical data derived from treated and control animals can be achieved.     

Pipette-tip selective extraction of glycoproteins with lectin modified gold nano-particles on a polymer monolithic phase

The in situ preparation of ethylene dimethacrylate porous polymer monoliths within 20 μL polypropylene pipette tips, bound via surface grafted methacrylate anchor sites, is reported. Gold nano-particles (AuNPs) were immobilised onto the monolith pore surface utilising azlactone chemistry and coverage verified using field emission scanning electron microscopy. Erythrina cristagalli lectin (ECL) was immobilised upon the attached AuNPs via a bio-functional linker. The ECL-modified tip was successfully applied for the enrichment of galactosylated protein (desialylated transferrin) versus a non-galactosylated protein (ribonuclease B) due to the specificity of ECL. Reversed-phase capillary HPLC was used to validate the efficiency and selectivity of the developed micro-extraction phase which resulted in an increase in extraction recovery of ～95% due to the AuNP enhanced surface area. Further specificity of the ECL-modified tip was demonstrated with a complex mixture of non-glycosylated and glycosylated proteins with differing terminal sugar structures. Finally, the lectin affinity phase was applied to a galactosylated glycoproteins spiked Escherichia coli cell lysate to successfully demonstrate matrix tolerance.     

Asymmetrical hippocampal connectivity in mesial temporal lobe epilepsy: evidence from resting state fMRI

Background

Recent studies have shown that the human right-hemispheric auditory cortex is particularly sensitive to reduction in sound quality, with an increase in distortion resulting in an amplification of the auditory N1m response measured in the magnetoencephalography (MEG). Here, we examined whether this sensitivity is specific to the processing of acoustic properties of speech or whether it can be observed also in the processing of sounds with a simple spectral structure. We degraded speech stimuli (vowel /a/), complex non-speech stimuli (a composite of five sinusoidals), and sinusoidal tones by decreasing the amplitude resolution of the signal waveform. The amplitude resolution was impoverished by reducing the number of bits to represent the signal samples. Auditory evoked magnetic fields (AEFs) were measured in the left and right hemisphere of sixteen healthy subjects.

Results

We found that the AEF amplitudes increased significantly with stimulus distortion for all stimulus types, which indicates that the right-hemispheric N1m sensitivity is not related exclusively to degradation of acoustic properties of speech. In addition, the P1m and P2m responses were amplified with increasing distortion similarly in both hemispheres. The AEF latencies were not systematically affected by the distortion.

Conclusions

We propose that the increased activity of AEFs reflects cortical processing of acoustic properties common to both speech and non-speech stimuli. More specifically, the enhancement is most likely caused by spectral changes brought about by the decrease of amplitude resolution, in particular the introduction of periodic, signal-dependent distortion to the original sound. Converging evidence suggests that the observed AEF amplification could reflect cortical sensitivity to periodic sounds.