Reactivity of Singlet Oxygen Toward Proteins: The Effect of Structure in Basic Pancreatic Trypsin Inhibitor and in Ribonuclease A

The reactions of singlet oxygen, ¹O₂, with large peptides have been described previously. It was found that even in these systems, which in their native form are generally not supposed to possess a stable structure in solution, the polypeptide does impede the access of ¹O₂ to the amino acids that react readily with ¹O₂. Here we describe the ¹0₂ reaction with two proteins of well-defined structure. The quenching of ¹O₂ by bovine pancreatic trypsin inhibitor (BPTI) and by ribonuclease A (RNase A) was compared to that of a solution at the same concentration as those of its constituent amino acids that react readily with ¹O₂. The proteins were studied in their native form, when partly denatured by splitting their S-S bonds and when fully denatured. It was found that while in the native form the quenching rate constant was seven times lower in BPTI (2.2 vs 15.2 times 10⁷WM^-1 s^-1) and three times lower in RNase A (11.0 vs 32 times 10⁷M^-l s^-1) than in a mixture of its constituent amino acid residues, it increased upon denaturation reaching in the fully denatured state the value of the corresponding amino acid mixture. More striking is the effect of the protein structure when comparing the fraction of the encounters between ¹O₂ and protein, which cause damage to the protein, as reflected in the decrease of its biological activity. This decrease is assumed to be due to the chemical (oxidative) reactions of ¹O₂ in the protein. In the exceptionally stable BPTI the fraction of such encounters was 0.05 and in RNase A it was 0.2, whereas for the amino acid tryptophan in solution, 0.7 of the collisions with ¹O₂ led to a chemical reaction.     

REACTIVITY OF SINGLET OXYGEN TOWARD LARGE PEPTIDES

Abstract— The reactions of singlet oxygen, ¹O₂, with amino acids and their derivatives have been studied previously. It was found that only five amino acid residues interact readily with ¹O₂. Here we describe its reactions with the large peptides melittin, neuropeptide Y (NPY) and insulin in their native and in their denatured forms. The singlet oxygen quenching by a polypeptide was compared with that of a solution at the same concentration as those of its constituent amino acids, which are known to react efficiently with ¹O₂. It was found that the quenching rate by such a mixture exceeded that of the polypeptides in their native form. The ratio of the rate constants for NPY to that of the corresponding amino acid mixture in solution was 0.75. For melittin in its monomeric form it was 0.83 and for a tetramer of melittin (at high ionic strength) it was 0.70. For native insulin the ratio of the rate constants was 0.55. For oxidized insulin with its -S-S- bridges opened the figure became 0.80. However, the quenching by all the polypeptides in their fully denatured form (in the presence of 6 M urea) equalled that of the corresponding amino acid mixtures. Although polypeptides are generally supposed not to possess a stable secondary structure in solution the effects are explained by shielding of some of the reactive amino acid residues in the chain by temporary folding or incipient secondary structures of the native polypeptide.
It is shown that the kinetics for a homogeneous solution of quenchers applies also to measurements in a polypeptide solution where the quenchers are localized along the polypeptide backbone and thus form clusters in solution.     

Near rings without zero divisors

Near rings without zero divisors, and a dual structure, near codomains, are studied. It is shown that a near ring is a near field if and only if it is an integral near ring, a near codomain, and has a non-zero distributive element. If the additive group (N, +) of a near integral domainN is cohopfian, then (N, +) possesses a fixed point free automorphism which is either torsion free or of prime order. This generalizes a well-known theorem of Ligh for finite near integral domains. A result ofGanesan [1] on the non-zero divisors in a finite ring is generalized to near rings.     

On systems of binomials in the ideal of a toric variety

Let be a toric set in the affine space . Given a set of binomials in the toric ideal of , we give a criterion for deciding the equality rad( ) = . This criterion extends to arbitrary dimension, and to arbitrary fields, an earlier result which concerned only monomial curves over an algebraically closed field of characteristic zero.

     

Invariant measures for algebraic actions, Zariski dense subgroups and Kazhdan's property

Let be any locally compact non-discrete field. We show that finite invariant measures for -algebraic actions are obtained only via actions of compact groups. This extends both Borel's density and fixed point theorems over local fields (for semisimple/solvable groups, resp.). We then prove that for -algebraic actions, finitely additive finite invariant measures are obtained only via actions of amenable groups. This gives a new criterion for Zariski density of subgroups and is shown to have representation theoretic applications. The main one is to Kazhdan's property for algebraic groups, which we investigate and strengthen.

     

Stochastic (white noise) analysis of resonant absorption in laser generated plasma

We suggest to use stochastic differential equations for laser-plasma problems. Using this technique we solve analytically the motion of the electrons at the critical layer and calculate the density profile scaling length (L). For an Nd laser flux of 10¹⁷ W/cm² we estimate L ≈ 0.15 μm, while for a CO₂ laser flux of 10¹⁵ W/cm² we get L ≈ 1.5 μm.     

Microspheres of Mixed Proteins

This paper describes the synthesis of mixed proteinaceous microspheres (MPMs) by the sonochemical method. The current fundamental research follows the research of Suslick and co‐workers who have developed a method by which high‐intensity ultrasound is used to make aqueous suspensions of proteinaceous microcapsules filled with water‐insoluble liquids. 1 By using high‐intensity ultrasound, we have synthesized microspheres made of a few different proteins. The three proteins used in the current experiments are bovine serum albumin (BSA), green fluorescent protein (GFP), and cyan fluorescent protein–glucose binding protein–yellow fluorescent fused protein (CFP‐GBP‐YFP). The two synthesized microspheres made of mixed proteins are BSA‐GFP and BSA‐(CFP‐GBP‐YFP). This paper presents the characterization of the sonochemically produced microspheres of mixed proteins. It also provides an estimate of the efficiency of the sonochemical process in converting the native proteins to microspheres.     

Kilohertz laser frequency sensing with Brillouin mutually modulated cross-gain modulation

Using mutually modulated cross-gain modulation, Stokes optical frequency changes are converted into modulation phase changes with high sensitivity. In the slow-light transition regime, we demonstrate kilohertz sensitivity to the Stokes optical carrier frequency. The sensitivity is inversely proportional to the modulation frequency of the pump and Stokes beams.