Rovibronic bands of the A<--X transition of CH3OO and CD3OO detected with cavity ringdown absorption near 1.2-1.4 microm

We have recorded several rovibronic bands of CH3OO and CD3OO in their A<--X transitions in the range of 1.18-1.40 microm with the cavity ringdown technique. While the electronic origins for these species have been reported previously, many newly observed rovibronic bands are described here. The experimental vibrational frequencies (given as nu in the unit cm(-1) in this paper) for the COO bending (nu8) and COO symmetric stretching (nu7) modes in the A state are 378 and 887 cm(-1) for CH3OO, and 348 and 824 cm(-1) for CD3OO, respectively. In addition, two other vibrational frequencies were observed for the A state of CD3OO, namely, nu5 (954 cm(-1)) and nu6 (971 cm(-1)). These experimental vibrational frequencies for the A state of both CH3OO and CD3OO are in good agreement with predictions from quantum-chemical calculations at the UB3LYP/aug-cc-pVTZ level. The enhanced activity of the nu5 vibrational mode in CD3OO is rationalized by mode mixing with the nu7 mode, as supported by calculations of multidimensional Franck-Condon factors. In addition, many hot bands involving the methyl torsional mode (nu12) are observed for both normal and deuterated methyl peroxy. These bands include the "typical" sequence transitions and some "atypical" ones due to the nature of the eigenvalues and eigenfunctions which are a consequence of the low, but very different, torsional barriers in the X and A states. In addition, the 12(2)2 band in CH3OO and the 12(3)3 band in CD3OO show quite different structures than the origin bands, an effect which results from tunneling splittings comparable to the rotational contour.     

A comparison of Tris-glycine and Tris-tricine buffers for the electrophoretic separation of major serum proteins

This paper compares different buffer systems for the electrophoretic separation of the five most abundant serum proteins on native-PAGE gel and cellulose membranes. A modified Tris-tricine system was shown to be superior for the separation of these serum proteins in a 7% m/v native-PAGE gel as compared with the traditionally used Tris-glycine and Tris-tricine methods. This modified Tris-tricine buffer system was also employed for the separation of serum proteins using a cellulose acetate membrane and very effective separation was observed as compared with the traditionally used Tris-barbital and Tris-glycine buffer systems.     

A study of oxaliplatin–nucleobase interactions using ion trap electrospray mass spectrometry

Oxaliplatin is an important anti-cancer drug that has been approved for the treatment of colorectal cancer. It is known that oxaliplatin, like other Pt-based drugs, interacts with DNA to form cytotoxic Pt-DNA adducts that disrupt important biological processes such as DNA replication and protein synthesis. Linear ion trap electrospray ionisation mass spectrometry (ESI-MS) was employed to study the interaction of oxaliplatin with DNA nucleobases. It was shown that oxaliplatin formed adducts with all four DNA nucleobases when present individually and in combination in solution. Multiple-stage tandem mass spectrometry (MSⁿ) enabled the fragmentation pathways of each adduct to be established. In addition, proposed structures for each product ion were obtained from the MS data. When all four bases were present together with the drug at near-equal molar concentrations, adducts containing predominantly adenine and guanine were formed, confirming that the drug preferentially binds to these nucleobases. A large molar excess of drug was required to ensure the formation of cytosine and thymine adducts in the presence of adenine and guanine. Even with a large excess of oxaliplatin, only mono-adducts of these nucleobases were observed when all four nucleobases were present. Figure Schematic of a linear ion trap mass spectrometer being used to isolate the diadduct of guanine with oxaliplatin showing the characteristic isotope pattern due to ¹⁹⁴Pt, ¹⁹⁵Pt and ¹⁹⁶Pt.     

Hydrodynamic and mass transfer studies in an external-loop air-lift bioreactor for immobilized animal cell culture

Air-lift bioreactors containing suspended or immobilized animal cells have been used for the production of a variety of high-value biologicals. In the bioprocessing industry, there is a need to study and quantify the relationships between bioreactor-system properties such as mixing, flow, mass transfer, and cell processes. In the present study, the performance of a 1-L external-loop air-lift bioreactor was investigated by studying gas-liquid oxygen transfer, mixing time, liquid velocity and gas hold-up at various aeration rates. These studies were performed over a range (0-25%) of loadings of small (500-800 μm) calcium alginate beads to investigate the effect of using various concentrations of cell immobilization matrices on the physical properties of the system. At an aeration rate of 0.5 vvm, the mixing time was decreased by 50%, from 75 s at 0% bead loading to 38 s at 10% bead loading. A minimum liquid velocity of 10 cm/s was required to keep the alginate beads in suspension. As bead loading increased, flow within the reactor went from turbulent conditions to the transition zone. At all bead loadings tested, the gas hold-up increased by only 2% with an increase in aeration rate from 0.1 to 1.0 vvm, regardless of whether the total reactor volume (i.e., liquid and beads) or the liquid volume was used in calculating the hold-up. A mathematical correlation was developed for expressing the dependence of the volumetric mass-transfer coefficient, k₁a, on aeration rate (vvm) and microbead loading. With this equation it was possible to predict, within 20%, the k₁a knowing the gas-flow rate and the volume percentage of microbeads present in the bioreactor. A theoretical study was also performed to calculate the oxygen transfer from the bulk liquid to the center of microcapsules containing animal cells using experimental k₁a data. The results suggest that whereas there is no oxygen limitation at 10 to 15% microcapsule loading, there is a potential mass-transfer problem at 25% loading if the bioreactor is operated at an aeration rate of less than 1.06 vvm.     

Amenability,critical exponents of subgroups and growth of closed geodesics

Let \(\Gamma \) be a (non-elementary) convex co-compact group of isometries of a pinched Hadamard manifold X. We show that a normal subgroup \(\Gamma _0\) has critical exponent equal to the critical exponent of \(\Gamma \) if and only if \(\Gamma /\Gamma _0\) is amenable. We prove a similar result for the exponential growth rate of closed geodesics on \(X/\Gamma \). These statements are analogues of classical results of Kesten for random walks on groups and Brooks for the spectrum of the Laplacian on covers of Riemannian manifolds.     

Operational Research in the U.K. in 1977: The Causes and Consequences of a Myth?

Instead of maintaining the original ideal of having a broad scientific basis for practical Operational Research, it is suggested that the O.R. community has uncritically accepted a myth which views O.R. as a "Hard" (Physical or even Mathematical) Science. It is argued that this has had profound consequences which explain the present difficulties O.R. workers have with problems involving major Social or Behavioural features. It is concluded that the "Hard" Science myth must be replaced, and a return made to the original conception of O.R., if we are to assist effectively in the complex social issues we face today.     

Tandem electrocatalytic CO2 reduction with Fe-porphyrins and Cu nanocubes enhances ethylene production

Copper-based tandem schemes have emerged as promising strategies to promote the formation of multi-carbon products in the electrocatalytic CO₂ reduction reaction. In such approaches, the CO-generating component of the tandem catalyst increases the local concentration of CO and thereby enhances the intrinsic carbon–carbon (C–C) coupling on copper. However, the optimal characteristics of the CO-generating catalyst for maximizing the C₂ production are currently unknown. In this work, we developed tunable tandem catalysts comprising iron porphyrin (Fe-Por), as the CO-generating component, and Cu nanocubes (Cucub) to understand how the turnover frequency for CO (TOF_CO) of the molecular catalysts impacts the C–C coupling on the Cu surface. First, we tuned the TOF_CO of the Fe-Por by varying the number of orbitals involved in the π-system. Then, we coupled these molecular catalysts with the Cu_cub and assessed the current densities and faradaic efficiencies. We discovered that all of the designed Fe-Por boost ethylene production. The most efficient Cu_cub/Fe-Por tandem catalyst was the one including the Fe-Por with the highest TOF_CO and exhibited a nearly 22-fold increase in the ethylene selectivity and 100 mV positive shift of the onset potential with respect to the pristine Cu_cub. These results reveal that coupling the TOF_CO tunability of molecular catalysts with copper nanocatalysts opens up new possibilities towards the development of Cu-based catalysts with enhanced selectivity for multi-carbon product generation at low overpotential.

Coupling the tunability of molecular catalysts and copper nanocatalysts opens up new possibilities towards the development of Cu-based catalysts with enhanced selectivity for multi-carbon product generation at low overpotential.     

Haulier Selection—An Application of the Analytic Hierarchy Process

A project to reduce the despatch costs of a manufacturer is described. This involved the construction of a model that would enable the lowest-cost haulier to be selected and answer the question of which of that haulier's depots should be used to handle the despatches. The existing information system did not generate the necessary data for the regular use of a model based on actual despatches. Furthermore, the pattern of demand was fairly volatile, so that the least-cost haulier might have been expected to change quite often. Therefore, the use of the analytic hierarchy process to derive the necessary data was explored. Attempts were made to compare the results of a complete census of traffic carried out in the initial stage of the project with the data obtained from the analytic hierarchy process.     

A Weil–Petersson type metric on spaces of metric graphs

In this note, we discuss an analogue of the Weil–Petersson metric for spaces of metric graphs and some of its properties.