The reaction of 1,2-dichloroethane with copper

The decomposition of 1,2-dichloroethane on polycrystalline copper has been studied using a microreactor. The reaction is found to have an activation energy of 81±5 kJ mol^–1 generating gaseous ethene and chemisorbed chlorine. The reaction terminates on completion of a monolayer of chemisorbed chlorine and is followed by a much slower reaction. The rate limiting step is thought to be C₂H₄Cl_2(phys)C2H₄Cl(_ads)+Cl_ads The reaction is compared with a UHV study of the same molecule on Cu(l 11) and the possibility of a negative ion transition state is discussed.     

The mechanism of the poisoning of ammonia synthesis catalysts by oxygenates O2, CO and H2O: an in situ method for active surface determination

The effect of adding an oxygenated poison (O₂, CO or H₂O) to a hydrogen/nitrogen stream producing ammonia over a triply promoted (K₂O, CaO, Al₂O₃) commercial catalyst is not unsurprisingly rapidly to poison the catalyst. However, immediately the oxygenated poison reacts with the catalyst and before total poisoning has occurred, which in these experiments took 10 min, there was an explosive release of ammonia producing concentrations in the gas phase in excess of the equilibrium value. This is thought to be due to a convulsive reorganisation of the surface of the catalyst in forming regions of an oxide overlayer, resulting in the expulsion of the standing surface nitrogen atom coverage as ammonia. However, in contradistinction to the observation of complete poisoning of the triply promoted catalyst shortly after switching the water (2.9%) into the hydrogen/nitrogen stream, when polycrystalline iron was used as the catalyst, after the initial pulse of ammonia was observed, the small quantity of water (2.9%) in the hydrogen/nitrogen stream resulted in an increased rate ( ×3) of ammonia synthesis which declined only slightly over the twenty minute duration of the experiment. The difference in behaviour between the triply promoted catalyst and the polycrystalline iron is thought to be due to the relative ease of reduction of the latter, so that submonolayer quantities of oxide can be stabilised on the surface of the polycrystalline iron. The promoting effect of this oxide overlayer is either structural or electronic; no distinction can be made from these experiments. The technique of injecting either O₂ or CO into a hydrogen/nitrogen stream which is producing ammonia over promoted catalysts in quantities insufficient to cause complete poisoning and measuring the oxygen coverage of the catalyst to a measured decrease in the ammonia synthesis rate, appears to be a ready, in situ method for the determination of the active catalyst area.     

The adsorption and decomposition of carbon dioxide on polycrystalline copper

The interaction of carbon dioxide with polycrystalline copper has been studied by radiolabelling techniques using {14-C} carbon dioxide, and by temperature programmed desorption. It is showninter alia, that: carbon dioxide is weakly adsorbed at the clean surface; that this acts as precursor which, on activation, produces adsorbed carbon monoxide and surface oxygen; and that this oxidised copper surface then adsorbs carbon dioxide more strongly yielding a state which can be hydrogenated first to formate, and thereafter to methanol.     

Ultrathin Dual‐Scale Nano‐ and Microporous Membranes for Vascular Transmigration Models

Selective cellular transmigration across the microvascular endothelium regulates innate and adaptive immune responses, stem cell localization, and cancer cell metastasis. Integration of traditional microporous membranes into microfluidic vascular models permits the rapid assay of transmigration events but suffers from poor reproduction of the cell permeable basement membrane. Current microporous membranes in these systems have large nonporous regions between micropores that inhibit cell communication and nutrient exchange on the basolateral surface reducing their physiological relevance. Here, the use of 100 nm thick continuously nanoporous silicon nitride membranes as a base substrate for lithographic fabrication of 3 µm pores is presented, resulting in a highly porous (≈30%), dual‐scale nano‐ and microporous membrane for use in an improved vascular transmigration model. Ultrathin membranes are patterned using a precision laser writer for cost‐effective, rapid micropore design iterations. The optically transparent dual‐scale membranes enable complete observation of leukocyte egress across a variety of pore densities. A maximal density of ≈14 micropores per cell is discovered beyond which cell–substrate interactions are compromised giving rise to endothelial cell losses under flow. Addition of a subluminal extracellular matrix rescues cell adhesion, allowing for the creation of shear‐primed endothelial barrier models on nearly 30% continuously porous substrates.     

An approach to studying scale for students in higher education: a Rasch measurement model analysis

A questionnaire comprising 80 self-report items was designed to measure student Approaches to Studying in a higher education context. The items were conceptualized and designed from five learning orientations: a Deep Approach, a Surface Approach, a Strategic Approach, Clarity of Direction and Academic Self-Confidence, to include 40 attitude items and 40 corresponding behavior items. The study aimed to create a scale and investigate its psychometric properties using a Rasch measurement model. The convenience sample consisted of 350 students at an Australian university in 1998. The analysis supported the conceptual structure of the Scale as involving studying attitudes and behaviors towards five orientations to learning. Attitudes are mostly easier than behaviors, in line with the theory. Sixty-eight items fit the model and have good psychometric properties. The proportion of observed variance considered true is 92% and the Scale is well-targeted against the students. Some harder items are needed to improve the targeting and some further testing work needs to be done on the Surface Approach. In the Surface Approach and Clarity of Direction in Studying, attitudes make a lesser contribution than behaviors to the variable, Approaches to Studying.     

Passive mechanical behavior of human neutrophils: effects of colchicine and paclitaxel

The role of microtubules in determining the mechanical rigidity of neutrophils was assessed. Neutrophils were treated with colchicine to disrupt microtubules, or with paclitaxel to promote formation of microtubules. Paclitaxel caused an increase in the number of microtubules in the cells as assessed by immunofluorescence, but it had no effect on the presence or organization of actin filaments or on cellular mechanical properties. Colchicine at concentrations <1.0 microM caused disruption of microtubular structures, but had little effect on either F-actin or on cellular mechanical properties. Higher concentrations of colchicine disrupted microtubular structure, but also caused increased actin polymerization and increases in cell rigidity. Treatment with 10 microM colchicine increased F-actin content by 17%, the characteristic cellular viscosity by 30%, the dependence of viscosity on shear rate by 10%, and the cortical tension by 18%. At 100 microM colchicine the corresponding increases were F-actin, 25%; characteristic viscosity, 50%; dependence of viscosity on shear rate, 20%; and cortical tension, 21%. These results indicate that microtubules have little influence on the mechanical properties of neutrophils, and that increases in cellular rigidity caused by high concentrations of colchicine are due to a secondary effect that triggers actin polymerization. This study supports the conclusion that actin filaments are the primary structural determinants of neutrophil mechanical properties.     

Measuring coping at a university using a Rasch model

Coping with academic difficulties at a university was based on six aspects: Motivation and Planning, Friends and Planning, Studying and Planning, Emotions, Spiritual Help and Coping by Doing Nothing. Stem-items for each aspect were conceptually ordered by difficulty. Each of the stem-items was answered from three perspectives, Good Coping Strategies, Actual Coping Strategies, and Stress Reduction Strategies. The three response categories were No, not on any occasion this semester; Yes, on 1 to 3 occasions this semester, and Yes, on 4 or more occasions this semester. The convenience sample was 337 students studying education at an Australian university and data were analysed with a Rasch measurement model. A scale was created in which the difficulties of the items were ordered from easy to hard and the student measures of Coping were ordered from low to high. Coping by Doing Nothing and Using Spiritual Help stem-items didn't fit the measurement model and were deleted. This left an effective item sample of 21 (7 stem-items times 3). The proportion of observed student variance considered true was 0.88. The results supported the theory behind the construct of Coping as using Motivation and Planning, Friends and Planning, Studying and Planning, and Emotions, in which Expected Good Coping Strategies are easier than Actual Coping Strategies which, in turn, are easier than Stress Reducing Coping Strategies.     

Tobacco etch virus protease: mechanism of autolysis and rational design of stable mutants with wild-type catalytic proficiency

Because of its stringent sequence specificity, the catalyticdomain of the nuclear inclusion protease from tobacco etch virus(TEV) is a useful reagent for cleaving genetically engineeredfusion proteins. However, a serious drawback of TEV proteaseis that it readily cleaves itself at a specific site to generatea truncated enzyme with greatly diminished activity. The rateof autoinactivation is proportional to the concentration ofTEV protease, implying a bimolecular reaction mechanism. Yet,a catalytically active protease was unable to convert a catalyticallyinactive protease into the truncated form. Adding increasingconcentrations of the catalytically inactive protease to a fixedamount of the wild-type enzyme accelerated its rate of autoinactivation.Taken together, these results suggest that autoinactivationof TEV protease may be an intramolecular reaction that is facilitatedby an allosteric interaction between protease molecules. Inan effort to create a more stable protease, we made amino acidsubstitutions in the P2 and P1' positions of the internal cleavagesite and assessed their impact on the enzyme's stability andcatalytic activity. One of the P1' mutants, S219V, was not onlyfar more stable than the wild-type protease (~100-fold), butalso a more efficient catalyst.