Modeling the reaction mechanisms for redox regulation of protein tyrosine phosphatase 1B activity

Protein tyrosine phosphatase 1B (PTP1B) functions by removing the phosphoryl group from tyrosinephosphorylated proteins in insulin signaling and metabolism. The regeneration of the active site involves a sulphenylamide intermediate derived from the intrastrand cross-linking between the catalytic serine and the neighboring backbone nitrogen. Two mechanisms have been proposed for the formation of the sulphenylamide intermediate and the subsequent reactivation of the catalytic site. In the current work, the proposed mechanisms have been investigated by the use of density functional theory calculations. Our results suggest that these two mechanisms have similar overall energy barriers and that the preferred route will be determined by the availability of hydrogen peroxide or other oxidizing reagents.     

An extremal problem related to probability

Summary We consider a walk from a stateA ₁ to a stateA _n+1 in which the probability of remaining atA _i isp _i , and the probability of progressing fromA _i toA _i+1 is 1 –p _i . The probabilityW _nk of reachingA _n+1 fromA ₁ in exactlyn + k steps can then be expressed as a polynomial of degreen + k in then variablesp ₁,,p _n . We determine the maximum value ofW _nk and the (unique) choice (p ₁,,p _n ) for which this extremum occurs.Dedicated to Professor Otto Haupt with best wishes on his 100th birthday     

The measure of non-normal sets

Summary It is well-known that almost every number in [0, 1] is normal in base 2, in the sense of Lebesgue measure. Kahane and Salem asked whether the same is true with respect to any Borel measure whose Fourier-Stieltjes coefficients vanish at infinity — in other words, whether the set of non-normal numbers is a set of uniqueness in the wide sense. We show that this is not the case. In fact, we give best-possible conditions on the rate of decay of in order that -almost every number be normal. The techniques include, on the one hand, probability measures with respect to which the binary digits in [0, 1] are independent only by blocks, rather than individually, and on the other hand, the strong law of large numbers for weakly correlated random variables.This work was partially supported by an NSF Graduate Fellowship, NSF Grant MCS-82-01602, and an AMS Research Fellowship.     

A new high-spin isomer in 39 97 Y58

An isomeric state at 3,523 keV excitation energy in⁹⁷Y with a half-life of 144(10) ms has been discovered with the fission-product separator JOSEF. This isomer is depopulated through aγ transition of 162 keV. AnE3 multipolarity for this transition is consistent with the measured conversion coefficients ofα _K =0.98(20) andα _T =1.00(19). Subsequent electromagnetic transitions populate several new⁹⁷Y levels which have high spins. For the isomer the three-quasiparticle configuration [πg _9/2?ν(h _11/2,g _7/2)]27/2^? is proposed. TheE3 transition with a strength about 2 single-particle units is supposed to be of the typeh ₁₁ ^2/+1 →d ₅ ^2/?1 . These findings provide evidence for the rapid shape transition atA?100 since they indicate shell-model character of ₃₉ ⁹⁷ Y₅₈ even at high excitation energies while the immediate neighbour ₃₉ ⁹⁸ Y₅₉ contains a rotational band based on a level at 495 keV.     

Rapid determination of ethylene glycol at toxic levels in serum and urine

The rapid gas chromatographic detection and determination of ethylene glycol in biological fluids is described. Phenylboronic acid in acetone was used for the esterification of glycol. The phenylboronates of ethylene glycol and 1,2-propylene glycol are not separated on a packed column of medium polarity (OV-17), but they can be separated on a non-polar column (OV-101). In both instances, 1,3-propylene glycol can be used as an internal standard. The method requires only 100 microliters of serum or urine and is suitable for trace analysis in an emergency toxicological laboratory. The utility of the method is demonstrated on two cases of human intoxication with ethylene glycol.     

Calorimeters for biotechnology

The isothermal and temperature scanning calorimeters manufactured by Calorimetry Sciences Corporation are briefly described. Applications of calorimetry to determine thermodynamics and kinetics of reactions of interest in biotechnology are described with illustrative examples.     

Identification of a highly effective asymmetric phase-transfer catalyst derived from α-methylnaphthylamine

A library of quaternary ammonium salts has been generated via reaction of simple chiral amines with a series of conformationally dynamic biphenyl units. Screening of this library against the alkylation of a glycine imine has led to the identification of a highly effective asymmetric phase-transfer catalyst derived from α-methylnaphthylamine.