CATALYTIC ACTION AND DESTRUCTION OF PROTOHEMATIN DURING PEROXIDE DEPENDENT LUMINOL CHEMILUMINESCENCE

Abstract— The catalytic action of protohematin was studied during the H₂O₂-dependent chemiluminescent luminol reaction. In spite of the fact that the catalyst was ultimately inactivated, the average protohematin molecule catalyzed the consumption of about 10³ molecules of luminol. The inactivation of catalyst and the initial consumption of luminol were studied during the luminescent reaction with different concentrations of reactants. A scheme accounting for the experimental observations is proposed. The formation of a primary protohematin-H₂O₂ complex is followed by binding of luminol, resulting in a ternary complex. A nucleophilic attack by a second molecule of H₂O₂ on the luminol molecule results in light emission from excited aminophthalate via a hypothetical peroxide adduct. The destruction of protohematin occurs via the attack of H₂O₂ on the porphyrin structure of the protohematin-H₂O₂ complex. Second order rate constants for the destruction of protohematin, the formation of the luminol complex and the nucleophilic attack of H₂O₂ are presented.     

Kinetic and thermodynamic study of adsorption of methylene blue and rhodamine B on adsorbent prepared from Hyptis suaveolens (Vilayti Tulsi)

In the present study adsorption behavior of methylene blue and rhodamine B from aqueous solution using adsorbent prepared from “Hyptis suaveolens” (Vilayti Tulsi) was investigated as a function of parameters such as initial concentration, adsorbent dose, pH, contact time and temperature. The adsorption process was pH dependent. The thermodynamic parameters such as $ {{\Updelta}}G,{{\Updelta}}H \,{\text{and}} \,{{\Updelta}}S $ were calculated to investigate the nature of adsorption, their values indicate that the adsorption process is favorable. The first-order, second-order and intra-particle diffusion models were used to describe the kinetic parameter. The Freundlich and Langmuir adsorption models were applied to describe the adsorption equilibrium. Column study was conducted for both dyes.     

Lithium bromide catalyzed solvent free method for synthesis of 2-substituted benzimidazoles and imidazopyridines

<正>The first successful lithium bromide mediated solvent free condensation of arylenediamine and esters to obtain 2-substituted benzimidazole and imidazopyridine in good to excellent yields is described.     

Stability study of somatropin by capillary zone electrophoresis

Human Growth Hormone (hGH) is a monomeric 22 kilo Dalton (kDa), 191 amino acid protein with an isoelectric point (pI) close to pH 5, produced in the anterior pituitary gland. High level production of somatropin (recombinant hGH) is done in Escherichia coli (E. coli) to meet the demand and to avoid possible Creutzfeldt-Jacob disease (CJD).The present study was initiated on the basis of results from post-marketing control of all somatropin preparations on the Norwegian market. The samples consisted of preparations presented as somatropin in solution, and some freeze-dried preparations were also included for comparison.The present study showed a significant degree of degradation of somatropin in solution. Deamidation increased over time for preparations in solution, as well as for freeze-dried preparations after dissolution. Preparations in solution showed high content of deamidated and cleaved forms. Freeze-dried preparations after dissolution and storage showed high content of deamidated forms, but low content of cleaved forms. Also, in one preparation, an unknown peak was detected in the electropherogram from capillary zone electrophoresis (CZE), eluting after the principal peak, in front of the Gln-18 somatropin peak.     

Moschusduft und Patchouliöl

Synthetic musk odours and patchouli oil are widely used in the production of cosmetics and scented household goods. In many perfumes one or both substances are key fragrances to create a unique and luxury odour. While patchouli oil is an essential oil from the patchouli plant, natural musk is historically an animal secrete which is derived from a gland of the muskdeer. The progress in organic synthesis has led to numerous synthetic musk‐like fragrance compounds. Both methods, the plant based production as well as the industrial synthesis of fragrances are connected to challenges such as ethic concerns and possible environmental risks. Therefore, sustainable chemical processes as well as biotechnological methods for the future production of important perfumery ingredients are developed.     

The time path of the marginal cost of oil: The turning point and the subsequent upward drift

The gradual exhaustion of existing deposits of a depletable non-renewable resource such as oil tends to shift the supply price curve of the resource upwards, increasing its marginal cost. Advances in technologies for exploration and production act as a brake on such upward shifts. Thus, there is a tug-of-war between the gradual exhaustion of existing deposits and technological progress. Using a recently developed constrained least-squares regression technique, we demonstrate that technological progress was the dominant force of the two during the first part of this century, causing a secular drop in marginal costs, but that this situation eventually was reversed, and that the gradual exhaustion of deposits gained the upper hand, causing marginal costs to increase. The turning point occurred around 1971–72. We also discuss the forecasting of the possible current upward drift of marginal costs.     

Analysis of colloidal particles V. size-exclusion chromatography of colloidal semiconductor particles

An HPLC technique for the size determination of colloidal cadmium sulphide and zinc sulphide in a diameter range from 20 down to 2 nm using silica with pore sizes from 30 to 100 nm is described. The growth of the particles during the run was suppressed by the addition of stabilizers to the eluent and by the use of reversed-phase silica as the stationary phase for inorganic stabilizers. The calibration of the column sets by electron microscopy resulted in a linear relationship between the logarithm of the particle diameter and the elution time. The analysis was carried out within 4–10 min. The lateral resolution lay between 1.3% for larger particles and 1.9% for smaller particles. Below a diameter of 13 nm these values were better than those found from electron microscopy. From the comparison of the calibration lines for various colloidal materials, the differences in their electrical double layers could be estimated. The limitations of the method are discussed and the size-exclusion chromatographic and electron microscopic methods are compared.     

N‐donor ligand as catalyst: A simple aza‐michael addition reaction in aqueous media

A novel approach for the Aza‐Michael addition reactions between various amines and α,β‐unsaturated esters, nitriles and ketones using N‐donor Ligand catalyst (3 mol %) is described. The reactions are carried out in aqueous media at an ambient temperature to afford the products in excellent yields.     

Novel,efficient,and green procedure for the synthesis of 1,5-benzodiazepines catalyzed by MgBr_2 in aqueous media

MgBr_2 performs as a novel catalyst for the synthesis of various 1,5-benzodiazepine derivatives from wide range of substituted ophenylenediamines and various ketones in good to excellent isolated yields(93-98%)using water as solvent at ambient temperature.Several solvents were examined for this reaction;however,in terms of reaction yield and time,water was found to be the optimum solvent.The remarkable advantages offered by this method are easily and inexpensive available catalyst,simple procedure,mild c...     

Exchanging heterogeneous goods via sealed bid auctions and transportation systems

A primary commodity such as wheat, rice, coffee, oil, etc., is shipped fromm locations where it was grown or pumped ton manufacturers. Each manufacturer processes, packages, advertises, and distributes the commodity under a consumer product brand name. The resulting heterogeneous good is sold at a sealed bid auction, in competition with the other manufacturers of the consumer product, tok final customers. The problem to be considered in this paper is to find a way of determining prices for the goods produced and the physical exchanges between seller and buyer which satisfy flow conditions and which take into account the evaluations of the goods by both sellers and buyers. The first model for doing this is given in section 1, which combines the idea of a sealed bid auction due to Shapley, Shubik and Thompson, with a conventional transportation system. The sealed bid auction is used to determine the exchange prices, and the transportation system is used to calculate the production and transportation costs. It is suggested that the resulting model type can also be applied in a wide range of problems that arise in the marketing of goods sold under brand names (i.e., heterogeneous goods) regardless of whether they are actually exchanged at formal auctions. We show in section 6 that our model is a generalization of the transshipment model in a recent paper by Dubey and Shapley [1]. In their model they considered a number of oligopolists engaged in transshipping and trading goods. Their oligopolists set their prices in order to maximize profits, rather than having them determined by an auction process as is done in our model. In section 7, we extend the model to one in which the wholesalers are permitted to make positive profits. We show how to calculate the values of coalitions of the various players in the model.The work of the first named author was prepared as part of the activities of the Management Sciences Research Group, Carnegie Mellon University, under Contract No. N00014-85-K-0198 NR 047-048 with the Office of Naval Research. Reproduction in whole or in part is permitted for any purpose of the U.S. Government.