Evidence of Structure Sensitivity in the Fischer–Tropsch Reaction on Model Cobalt Nanoparticles by Time-Resolved Chemical Transient Kinetics

The Fischer–Tropsch process, or the catalytic hydrogenation of carbon monoxide (CO), produces long chain hydrocarbons and offers an alternative to the use of crude oil for chemical feedstocks. The observed size dependence of cobalt (Co) catalysts for the Fischer–Tropsch reaction was studied with colloidally prepared Co nanoparticles and a chemical transient kinetics reactor capable of measurements under non-steady-state conditions. Co nanoparticles of 4.3 nm and 9.5 nm diameters were synthesized and tested under atmospheric pressure conditions and H₂/CO=2. Large differences in carbon coverage (Θ_C) were observed for the two catalysts: the 4.3 nm Co catalyst has a Θ_C less than one while the 9.5 nm Co catalyst supports a Θ_C greater than two. The monomer units present on the surface during reaction are identified as single carbon species for both sizes of Co nanoparticles, and the major CO dissociation site is identified as the B₅-B geometry. The difference in activity of Co nanoparticles was found to be a result of the structure sensitivity caused by the loss of these specific types of sites at smaller nanoparticle sizes.     

Lp-estimates for the nonlinear spatially homogeneous Boltzmann equation

This paper studies L^p-estimates for solutions of the nonlinear, spatially homogeneous Boltzmann equation. The molecular forces considered include inverse k^th-power forces with k > 5 and angular cut-off.The main conclusions are the following. Let f be the unique solution of the Boltzmann equation with f(v,t)(1 + ¦v²¦)^(s ₁ ^{+ /p)/2} L¹, when the initial value f ₀ satisfies f ₀(v) 0, f ₀(v) (1 + ¦v¦²)^(s ₁ ^{+ /p)/2} L¹, for some s₁ 2 + /p, and f ₀(v) (1 + ¦v¦²)^s/2 L^p. If s 2/p and 1 < p < , then f(v, t)(1 + ¦v¦²)^{(s s} ₁)^/2 L^p, t > 0. If s >2 and 3/(1+ ) < p < , thenf(v,t) (1 + ¦v¦²)^(s(s ₁ ^{+ 3/p))/2} L^p, t > 0. If s >2 + 2C₀/C₁ and 3/(l + ) < p < , then f(v,t)(1 + ¦v¦²)^s/2 L^p, t > 0. Here 1/p + 1/p = 1, x y = min (x, y), and C₀, C₁, 0 < 1, are positive constants related to the molecular forces under consideration; = (k – 5)/ (k – 1) for k^th-power forces.Some weaker conclusions follow when 1 < p 3/ (1 + ).In the proofs some previously known L-estimates are extended. The results for L^p, 1 < p < , are based on these L-estimates coupled with nonlinear interpolation.     

Polynomials: a theme which should not be forgotten

There is a definite movement to remove many of the topics concerning polynomials from the school curriculum. The purpose of this paper is to point out why this movement is misguided and should be reversed.     

Structural Manipulation of Ruthenium(II) Polypyridine Nitrone Complexes to Generate Phosphorogenic Bioorthogonal Reagents for Selective Cellular Labeling

We report a new class of ruthenium(II) polypyridine complexes functionalized with a nitrone group as phosphorogenic bioorthogonal probes. These complexes were very weakly emissive owing to rapid C=N isomerization of the nitrone moiety, but exhibited significant emission enhancement upon strain‐promoted alkyne–nitrone cycloaddition (SPANC) reaction with bicyclo[6.1.0]nonyne (BCN)‐modified substrates. The modification of nitrone with a dicationic ruthenium(II) polypyridine unit at the α‐C‐position and a phenyl ring at the N‐position led to remarkably accelerated reaction kinetics, which are substantially greater (up to ≈278 fold) than those of other acyclic nitrone–BCN systems. Interestingly, the complexes achieved specific cell membrane/cytosol staining upon specific labeling of an exogenous substrate, BCN‐modified decane (BCN‐C10), in live cells. Importantly, the in situ generation of the more lipophilic isoxazoline adduct in the cytoplasm resulted in increased cytotoxicity, highlighting a novel approach to apply the SPANC labeling technique in drug activation.     

Magnetic Flux Lines in Complex Geometry Type-II Superconductors Studied by the Time Dependent Ginzburg-Landau Equation

The time-dependent Ginzburg-Landau equation is solved numerically for type-II superconductors of complex geometry using the finite element method. The geometry has a marked influence on the magnetic vortex distribution and the vortex dynamics. We have observed generation of giant vortices at boundary defects, suppressing the superconducting state far into the superconductor.     

Threshold effects on renormalization group running of neutrino parameters in the low-scale seesaw model

We show that, in the low-scale type-I seesaw model, renormalization group running of neutrino parameters may lead to significant modifications of the leptonic mixing angles in view of so-called seesaw threshold effects. Especially, we derive analytical formulas for radiative corrections to neutrino parameters in crossing the different seesaw thresholds, and show that there may exist enhancement factors efficiently boosting the renormalization group running of the leptonic mixing angles. We find that, as a result of the seesaw threshold corrections to the leptonic mixing angles, various flavor symmetric mixing patterns (e.g., bi-maximal and tri-bimaximal mixing patterns) can be easily accommodated at relatively low energy scales, which is well within the reach of running and forthcoming experiments (e.g., the LHC).     

Proficiency testing in analytical chemistry, microbiology and laboratory medicine: working discussions on current practice and future directions

A summary of the working group (WG) discussions on proficiency testing (PT) and external quality assessment (EQA) held at the Eurachem Workshop, Rome, 5–7 October 2008 is provided. The eight WG’s covered a range of issues concerned with current practice and future directions; how frequently should laboratories participate in PT/EQA? (WG1); developments in PT/EQA within the EU—what is required in future? (WG2); what issues do developing countries face with regards to PT/EQA? (WG3), what issues are specific to microbiology PT/EQA? (WG4); what new fields are emerging for PT/EQA? (WG5); what will be the impact of the new ISO/IEC 17043 standard? (WG6); do current PT/EQA schemes meet the needs of participants? (WG7); and what are the issues that affect the quality of proficiency test items? (WG8). Delegates with different backgrounds were on each WG in order to capture a range of views and experience from a number of different sectors. Working group representatives included PT/EQA providers, participants in PT/EQA schemes and end users of PT results such as accreditation bodies and regulatory authorities, from countries around the world.     

The off-line group seat reservation problem

In this paper we address the problem of assigning seats in a train for a group of people traveling together. We consider two variants of the problem. One is a special case of two-dimensional knapsack where we consider the train as having fixed size and the objective is to maximize the utilization of the seats in the train. The second is a special case of two-dimensional bin packing where all requests must be accommodated while trying to minimize the number of passenger cars needed. For both variants of the problem we present a number of bounds and develop exact algorithms. Computational results are presented for various instances based on realistic data, and from the packing literature adapted to the problems addressed.     

Mercerized cellulose biocomposites: a study of influence of mercerization on cellulose supramolecular structure, water retention value and tensile properties

In this study the effect of the mercerization degree on the water retention value (WRV) and tensile properties of compression molded sulphite dissolving pulp was evaluated. The pulp was treated with 9, 10, or 11 % aqueous NaOH solution for 1 h before compression molding. To study the time dependence of mercerization the pulp was treated with 12 wt% aqueous NaOH for 1, 6 or 48 h. The cellulose I and II contents of the biocomposites were determined by solid state cross polarization/magic angle spinning carbon 13 nuclear magnetic resonance (CP/MAS ¹³C NMR) spectroscopy. By spectral fitting of the C6 and C1 region the cellulose I and II content, respectively, could be determined. Mercerization decreased the total crystallinity (sum of cellulose I and cellulose II content) and it was not possible to convert all cellulose I to cellulose II in the NaOH range investigated. Neither increased the conversion significantly with 12 wt% NaOH at longer treatment times. The slowdown of the cellulose I conversion was suggested as being the result from the formation of cellulose II as a consequence of coalescence of anti-parallel surfaces of neighboring fibrils (Blackwell et al. in Tappi 61:71–72, 1978; Revol and Goring in J Appl Polym Sci 26:1275–1282, 1981; Okano and Sarko in J Appl Polym Sci 30:325–332, 1985). Compression molding of the partially mercerized dissolving pulps yielded biocomposites with tensile properties that could be correlated to the decrease in cellulose I content in the pulps. Mercerization introduces cellulose II and disordered cellulose and lowered the total crystallinity reflected as higher water sensitivity (higher WRV values) and poorer stiffness of the mercerized biocomposites.     

Cerebral abnormalities in Wilson''s disease as evaluated by ultra-low-field magnetic resonance imaging and computerized image processing

The cerebral involvement of a 13-yr-old boy with Wilson's disease was serially evaluated during the first 18 mo of D-penicillamine treatment. An ultra-low-field magnetic resonance imaging (ULF MRI) system, operating at 0.02 T, with computerized image processing was used. The half-yr period prior to the clinical diagnosis was set, the patient had showed poor school performance, emotional lability, deteriorating handwriting, progressively slow, gross, and fine motor functions, and a fixed rigid smile. No overt signs of liver disease were found. With D-penicillamine treatment (1–1.5 g/d) a continuous improvement was seen. The pretreatment MRI investigation showed pronounced pathological transformation in the basal ganglia. However, changes were seen also in most other parts of the brain indicating diffuse involvement. During treatment the computerized MR images became gradually more normal. The current magnetic resonance imaging system with computerized image processing is a sensitive and simple method for evaluation of subtle parenchymal changes of the brain.