Insights into the Relationship of Catalytic Activity and Structure: A Comparison Study of Three Carbonic Anhydrase Mimics

Density functional theory (DFT) calculations were used to study the mechanism of CO₂ hydrolysis by Zn‐(1,5,9‐triazacyclododecane) and Zn‐cyclam and evaluate the associated thermodynamic and kinetic parameters. Microkinetic models were then built based on the kinetics and thermodynamics derived from first principles. Both catalysts showed very similar behavior to Zn‐cyclen, which we have reported previously, but with multiple distinctions. The intrinsic reaction rate constants for Zn‐(1,5,9‐triazacyclododecane) and Zn‐cyclam were calculated to be 2693 and 4623 M^?1 s^?1, respectively, which is in reasonable agreement with experimental values reported or estimated. The CO₂ adsorption step was found to be a rate‐limiting step for all three catalysts. Zn‐cyclam has the lowest barrier for this step due to the highest pK_a or nucleophilicity of the Zn‐OH^? form, and_, therefore, the highest intrinsic activity. However, the observed reaction rate constant also depends on the availability of the catalyst. The decrease in the observed reaction rate constant over 0–12 ms was ascribed to the decrease in the concentration of the catalytic form, Zn‐OH^?, which was primarily converted to Zn‐HCO₃^?. The reaction rate constant of Zn‐cyclam dropped much faster than those of Zn‐cyclen and Zn‐(1,5,9‐triazacyclododecane) due to lower energy of the Zn‐HCO₃^? form. The conversion of CO₂ at 1000 ms as a function of pH was calculated to compare the relative activity of these catalysts, and Zn‐cyclen was found to be the best catalyst.     

Preliminary communication Liquid crystalline cardanyl β-D-glucopyranosides

Two novel aryl glycosides were synthesized, which varied in the extent of unsaturation in the lipophilic part, from plant/crop-based renewable resource materials. Their liquid crystalline properties were characterized by optical polarizing microscopy, differential scanning calorimetry and X-ray diffraction. All the mesophases are identified as lamellar in structure.     

Online Cooperative Learning in Physical Chemistry

The use of cooperative learning in an online setting is examined using the online segment of a recently offered physical chemistry course as an example. The nature and function of classical, face-to-face cooperative learning are outlined. The online course segment is outlined and is analyzed with regard to the criteria for classical cooperative learning. Though this specific course segment functioned poorly when taught as online cooperative learning, it is possible to structure online courses to take advantage of the strengths of cooperative learning. The possible structure and function of an online cooperative learning community are explored, concluding with a specific model for online cooperative learning.     

Lavrentiev's regularization method for nonlinear ill-posed equations in Banach spaces

In this paper, we deal with nonlinear ill-posed problems involving m-accretive mappings in Banach spaces. We consider a derivative and inverse free method for the implementation of Lavrentiev regularization method. Using general H¨older type source condition we obtain an optimal order error estimate. Also we consider the adaptive parameter choice strategy proposed by Pereverzev and Schock(2005) for choosing the regularization parameter.     

Evard Immanuel Hjelt (1855–1921): Finnish Chemist and Historian of Chemistry

Although today unjustly neglected abroad and often even in his native land, Edvard Immanuel Hjelt (1855–1921), was an exceptionally gifted, dedicated, and multifaceted individual who made important contributions to chemistry, the history of chemistry, politics, and the management of national and international affairs. Little information about him is available in English. The present article supplements the only two English sources available [1, pp 66–83; 2] and makes this chemist-statesman better known to those chemists and historians who do not read Swedish or Finnish.In this section we present articles by leading scientific historians that chronicle the important events, persons, and publications that make up the rich history of chemical science. The history, and the articles in this ection often make that very clear. Chemists and their research are always influenced by current events. These articles are intended to describe the setting in which important discoveries occurred and to humazine their discoveres.     

NANOSECOND KINETIC ABSORPTION AND CALORIMETRIC STUDIES OF CYCLOPENTENONE: THE TRIPLET, SELF-QUENCHING, AND THE PREDIMERIZATION BIRADICALS

The photolysis of 2-cyclopentenone has been studied by a combination of kinetic absorption spectrophotometry and time-resolved photoacoustic calorimetry. The lifetime of the cyclopentenone triplet is strongly concentration dependent and corresponds to a value of 380 +/- 75 ns at infinite dilution in acetonitrile. The biradical intermediate (or pair of isomeric biradicals) immediately preceding formation of photodimer forms with very high efficiency upon quenching of triplet cyclopentenone by a second ground state cyclopentenone molecule and has an energy of 47 kcal/mol relative to two molecules of reactant. Quenching of the cyclopentenone triplet by conjugated dienes is much slower than expected, which is the reason that early estimates of the triplet lifetime were much too short.     

Victor Moritz Goldschmidt (1888–1947): A Tribute to the Founder of Modern Geochemistry on the Fiftieth Anniversary of His Death

Goldschmidt combined a number of widely separated sciences to synthesize a new structural crystal chemistry. Although his work on the relative abundances of the elements, atomic and ionic radii, interionic distances, the effect of radius ratio on coordination number in crystals, replacement of ions in minerals, and the lanthanide contraction is found in almost every textbook of general and inorganic chemistry and has provided the basis for modern crystal chemistry and the use of size relationships for interpreting properties of inorganic substances, Goldschmidts name, life, and career remain relatively unknown to most chemical educators and practicing chemists.Goldschmidt used the basic properties of matter to provide simple and elegant explanations for the composition of our environment. Throughout his relatively brief career, filled with sorrow and tragedy, he continued to maintain his intense interest in the elements and their genesis, affinities, and associations despite his changes from one method to another in his attempts to obtain new and more complete data. Thus, although he used petrology, crystallography, and chemistry and enriched all these fields greatly, to him they were only tools for exploring the earth and its history.