Chloromethane surface chemistry on Fe3O4(1 1 1)-(2 × 2): A thermal desorption spectrometry comparison of CCl4, CBr2Cl2, and CH2Cl2

The surface chemistry of CBr₂Cl₂ on the Fe₃O₄(1 1 1)-(2 × 2) selvedge of single-crystal α-Fe₂O₃(0 0 0 1) has been investigated using temperature programmed reaction and desorption (TPR/D) measurements. The spectra obtained in this case show that strong chemisorption occurs and that a series of adsorbed halogenated reaction products are present. By comparison, studies of the adsorbed phase of CH₂Cl₂ show that only physisorption occurs. The TPR/D spectra of CBr₂Cl₂ show that dissociative formation of CCl₂ followed by its reaction with lattice oxygen is central to the monolayer reaction chemistry in this chloromethane. The branching ratios of the various desorbed products are compared with those obtained from CCl₄ adsorbed on the same (2 × 2) surface.     

Rational design of a beta-lactamase inhibitor achieved via stabilization of the trans-enamine intermediate: 1.28 A crystal structure of wt SHV-1 complex with a penam sulfone

beta-Lactamases are one of the major causes of antibiotic resistance in Gram negative bacteria. The continuing evolution of beta-lactamases that are capable of hydrolyzing our most potent beta-lactams presents a vexing clinical problem, in particular since a number of them are resistant to inhibitors. The efficient inhibition of these enzymes is therefore of great clinical importance. Building upon our previous structural studies that examined tazobactam trapped as a trans-enamine intermediate in a deacylation deficient SHV variant, we designed a novel penam sulfone derivative that forms a more stable trans-enamine intermediate. We report here the 1.28 A resolution crystal structure of wt SHV-1 in complex with a rationally designed penam sulfone, SA2-13. The compound is covalently bound to the active site of wt SHV-1 similar to tazobactam yet forms an additional salt-bridge with K234 and hydrogen bonds with S130 and T235 to stabilize the trans-enamine intermediate. Kinetic measurements show that SA2-13, once reacted with SHV-1 beta-lactamase, is about 10-fold slower at being released from the enzyme compared to tazobactam. Stabilizing the trans-enamine intermediate represents a novel strategy for the rational design of mechanism-based class A beta-lactamase inhibitors.     

Photoinduced-reaction dynamics of halogenated alkanes on iron oxide surfaces: CH3I on Fe3O4(111)-(2x2)

The adsorption, thermal chemistry, and photoreaction dynamics of methyl iodide on the (2x2) magnetite termination of natural single-crystal hematite have been investigated by time-of-flight quadrupole mass spectrometry (TOF-QMS), temperature-programmed desorption (TPD) and Auger electron spectroscopy (AES). The methyl iodide thermal desorption spectra, taken after dosing the (2x2) surface at 100 K with CH(3)I, show a multiple-peak coverage-dependent behavior, consistent with the presence of several distinct adsorbed phases, along with defect-mediated dissociative chemisorption in the first monolayer. At >1 ML, methyl iodide forms a metastable physisorbed second layer, which desorbs at 148 K, but at higher coverage converts to a layer, which desorbs at 170 K. In the presence of low-fluence-pulse irradiation at 248 nm, angle-resolved TOF-QMS measurements show that 1.6 and 0.3 eV CH(3) fragments are ejected from the adsorbate surface; these fragments originate from direct photodissociation and dissociative photoinduced electron transfer, respectively. These energetic photoejected fragments have characteristic angular distributions peaked at approximately 0 degree with respect to the surface normal. These results and the coverage-dependent relative intensities suggest that the predominant orientation in the first monolayer of the adsorbed CH(3)I is normal to the crystal plane.     

Evaluation of manganese and oxygen content in La0.7Sr0.3MnO3−δ and correlation with the thermodynamic data

In order to understand how the thermodynamic properties are related to the oxygen and manganese content in the Sr-doped lanthanum manganites, nonstoichiometric perovskite phases La_0.7Sr_0.3MnO_3−δ have been investigated by using solid state electrochemical techniques, as well as wet chemical methods. The influence of the oxygen stoichiometry change on the thermodynamic properties was examined using the data obtained by a coulometric titration technique coupled with solid state electromotive force measurements (EMF). The results were correlated with the average Mn valence values as determined by a chemical method based on two independent iodometric titrations, with amperometric dead-stop end point detection. New features related to the relationship between the average Mn valence, the oxygen nonstoichiometry variation, and the thermodynamic behavior were evidenced.