Practical preparation and deblocking conditions for N-alpha-(2-(p-biphenylyl)-2-propyloxycarbonyl)-amino acid (N-a-Bpoc-Xxx-OH) derivatives

Reproducible preparations are given for salts of the following L-amino acid derivatives: Bpoc-Ala-OH, Bpoc-Arg(Mtr)-OH, Bpoc-Asn-OH, Bpoc-Asp(OtBu)-OH, Bpoc-Cys(Acm)-OH, Bpoc-Cys(S-tBu)-OH, Bpoc-Gln-OH, Bpoc-Glu(OtBu)-OH, Bpoc-Gly-OH, Bpoc-Ile-OH, Bpoc-Leu-OH, N-alpha-Bpoc-Lys(epsilon-Boc)-OH, Bpoc-Met-OH, Bpoc-Phe-OH, Bpoc-Pro-OH, Bpoc-Ser(OtBu)-OH, Bpoc-Thr(OtBu)-OH, Bpoc-Tyr-OH, Bpoc-Val-OH. A study of the deblocking of N-alpha-Bpoc peptides in dichloromethane containing 0.5% trifluoroacetic acid revealed that a rapid equilbrium is established between the first-formed monomeric alkene 2-p-biphenylylpropene and the hindered dimer 2,4-bis(p-biphenylyl)-4-methyl-1-pentene. Thioethers were found to be inefficient carbocation scavengers for the deblocking reaction. The most efficient scavengers were found to be thiophenol and benzyl mercaptan, and the following approximate reactivity order was established: benzyl mercaptan approximately thiophenol greater than indole much greater than 1,3-dimethoxybenzene approximately resorcinol greater than 1,3,5-trimethoxybenzene approximately dimethyl sulfide approximately thioanisole.     

Diffusion Boundary Layers Ameliorate the Negative Effects of Ocean Acidification on the Temperate Coralline Macroalga Arthrocardia corymbosa

Anthropogenically-modulated reductions in pH, termed ocean acidification, could pose a major threat to the physiological performance, stocks, and biodiversity of calcifiers and may devalue their ecosystem services. Recent debate has focussed on the need to develop approaches to arrest the potential negative impacts of ocean acidification on ecosystems dominated by calcareous organisms. In this study, we demonstrate the role of a discrete (i.e. diffusion) boundary layer (DBL), formed at the surface of some calcifying species under slow flows, in buffering them from the corrosive effects of low pH seawater. The coralline macroalga Arthrocardia corymbosa was grown in a multifactorial experiment with two mean pH levels (8.05 ‘ambient’ and 7.65 a worst case ‘ocean acidification’ scenario projected for 2100), each with two levels of seawater flow (fast and slow, i.e. DBL thin or thick). Coralline algae grown under slow flows with thick DBLs (i.e., unstirred with regular replenishment of seawater to their surface) maintained net growth and calcification at pH 7.65 whereas those in higher flows with thin DBLs had net dissolution. Growth under ambient seawater pH (8.05) was not significantly different in thin and thick DBL treatments. No other measured diagnostic (recruit sizes and numbers, photosynthetic metrics, %C, %N, %MgCO₃) responded to the effects of reduced seawater pH. Thus, flow conditions that promote the formation of thick DBLs, may enhance the subsistence of calcifiers by creating localised hydrodynamic conditions where metabolic activity ameliorates the negative impacts of ocean acidification.     

A multinuclear NMR study of 2,3-bisphosphoglycerate metabolism in the human erythrocyte

Resonances from 13C, 31P and 1H have been detected simultaneously in suspensions of human erythrocytes using a modified NMR spectrometer equipped with a probe tuned to four different frequencies. The utility of multinuclear NMR in the study of cellular metabolism is demonstrated with an investigation of 13C label flux through the 2,3-bisphosphoglycerate bypass in human erythrocytes. In a single experiment, the respective contributions of this bypass and the pentose-phosphate shunt were found to be 27 and 10% of the total glycolytic rate.     

Observations on the biology of the potato-root eelworm, Heterodera schachtii Schmidt

Results are presented of experiments on the effect of low temperature and of soil type upon the potato-root eelworm, Heterodera schachtii.
In some experiments exposure of cysts, to low temperatures had a definite lethal effect, but in others the cysts were unharmed. The reason for this variation was not apparent. Exposure of the larvae of die nematode to even a relatively slight degree of frost resulted in the death of the larvae, provided mat die surrounding medium was completely frozen. In this respect the larvae appear to differ markedly from those of the beet strain of H. schachtii. That the larvae had actually been killed was shown by the fact that they produced no cysts on the roots of potato plants and also by their almost immediate absorption of iodine.
It was confirmed that H. schachtii cysts produced on the roots of potato plants grown in a heavy medium are smaller in size and fewer in number than those formed on the roots of plants grown in a light medium. The heavy medium used was pure clay, the light one pure sand, while equal numbers of eelworm larvae served in each case as inoculum. The difference in cyst size was significant, and fewer larvae emerged from the cysts formed in clay than from those produced in sand.     

Stimulation of larval emergence in Heterodera schachtii Schmidt, by certain concentrations of silver compounds

Certain dilute solutions of organic silver compounds, e.g. 0.001% silver proteinate, acting for a short time on cysts of the potato strain of Heterodera schachtii , cause increased numbers of larvae to emerge from the cysts when the latter are transferred to potato root excretion. More prolonged exposure of cysts to these solutions tends to result in a toxic effect which is also produced by more concentrated solutions. It is concluded that many more eggs in H. schachtii cysts are mature and capable of hatching than can be accounted for by ordinary larval liberation brought about by means of root excretion alone. Increasing periods of pre-treatment of cysts in tap water tend to produce increases in larval emergence, although this stimulation is probably of a different type from that given by silver compounds.