A Molecular Perspective on the d-Band Model: Synergy Between Experiment and Theory

The d-band model of Hammer and Nørskov (Nature 376:238, 1995 [3]) relating adsorption energies to the d-band position, and the adsorption energies to barriers in catalytic reactions, has been extremely successful in predicting reactivities and catalysts. In the present contribution we review recent combined experimental and theoretical work on chemical bond-formation at surfaces. We focus on the adsorbate and how the adsorbate electronic structure can be rehybridized through mixing with unoccupied states to generate the radical state, real or virtual, that can then form electron pairs with the metal d-states, as described by the d-band model. We discuss five important bonding situations: (i) atomic radical, (ii) diatomics with unsaturated π-systems (Blyholder model), (iii) unsaturated hydrocarbons (Dewar–Chatt–Duncanson model), (iv) lone–pair interactions, and (v) saturated hydrocarbons (physisorption). Where the d-band model predicts trends along the series of transition metals, the present work provides intuitive tools for predicting trends among different adsorbates.     

Crystal formation involving 1-methylbenzimidazole in iodide/triiodide electrolytes for dye-sensitized solar cells

Nitrogen heterocyclic compounds, such as N-methylbenzimidazole (MBI), are commonly used as additives to electrolytes for dye-sensitized solar cells (DSCs), but the chemical transformation of additives in electrolyte solutions remains poorly understood. Solid crystalline compound (MBI)₆(MBI-H⁺)₂(I⁻)(I₃⁻) (1) was isolated from different electrolytes for DSCs containing MBI as additive. The crystal structure of 1 was determined by single-crystal X-ray diffraction. In the crystal structure, 1 contains neutral and protonated MBI fragments; iodide and triiodide anions form infinite chains along the crystallographic a-axis. The role of the solvent and additives in the crystallization process in electrolytes is discussed.     

Relationships between milking frequency, lactation persistency and milk yield in Swedish Red heifers and cows milked in a voluntary attendance automatic milking system

A large dataset comprising output from an automatic milking (AM) system between 1999 and 2006 was examined and a total of 172 cow lactation curves and 68 heifer lactation curves were identified for further analysis. Relationships between milking frequency at different stages of lactation and lactation persistency and total lactation yield were determined. Cows had higher peak and total milk yields than heifers, but heifers had higher persistency (defined as the rate of decline in milk yield between days 100 and 300 post calving). Milking frequency did not differ significantly between cows and heifers in early lactation, but thereafter decreased significantly more in cows than in heifers. The effect of milking frequency on yield characteristics was analysed by comparing the highest and lowest quartiles for milking frequency. High milking frequency in early lactation was consistently associated with increased peak yield. High milking frequency averaged across the whole lactation was associated with increased peak yield in both cows and heifers, and with improved lactation persistency in cows only. This resulted in total lactation yield that was 21% greater in the high quartile cows compared with the low.     

Cellulose‐Based Ionogels for Paper Electronics

A new class of biofriendly ionogels produced by gelation of microcellulose thin films with tailored 1‐ethyl‐3‐methylimidazolium methylphosphonate ionic liquids are demonstrated. The cellulose ionogels show promising properties for application in flexible electronics, such as transparency, flexibility, transferability, and high specific capacitances of 5 to 15 μF cm^?2. They can be laminated onto any substrate such as multilayer‐coated paper and act as high capacitance dielectrics for inorganic (spray‐coated ZnO and colloidal ZnO nanorods) and organic (poly[3‐hexylthiophene], P3HT) electrolyte‐gated field‐effect transistors (FETs), that operate at very low voltages (<2 V). Field‐effect mobilities in ionogel‐gated spray‐coated ZnO FETs reach 75 cm² V^?1 s^?1 and a typical increase of mobility with decreasing specific capacitance of the ionogel is observed. Solution‐processed, colloidal ZnO nanorods and laminated cellulose ionogels enable the fabrication of the first electrolyte‐gated, flexible circuits on paper, which operate at bending radii down to 1.1 mm.     

Fuel quality changes during seasonal storage of compacted logging residues and young trees

Forest fuel procurement creates logistical problems, as large stocks are accumulated along the supply chain. The purpose of this study was to examine fuel quality (moisture content, ash content and calorific value) of compacted young trees (mainly downy birch) and both uncompacted and compacted logging residues (LR) (mainly Norway spruce). The materials were examined before and after storage, with and without cover, and effects of handling were considered. Dry matter losses from compacted LR during storage and handling were determined. Fuel quality and mass were determined before and after storage and handling. The moisture content of LR dropped to 28.6% when stored in small piles after fuel adapted logging at the clear felling site for 3 weeks in May. Drying continued after compaction into cylindrical bales (length 3.4 m, diameter 0.7 m) and during storage in windrows (9 and 12 months), the moisture content falling to 18.2–20.7% for the covered and 18.8–24.9% for the uncovered material. The windrow of loose LR remoistened to 40.8% (by snow contamination) resulted in a 6% lower net calorific value as received, compared to cylindrical bales. Ash contents were in the range 1.6–2.2% for LR and 1.0–1.2% for young trees. Dry matter losses ranged from 8.4% to 18.1% on compacted LR. Remoistening during the winter is higher for loose than for compacted LR. Early summer in northern Sweden provides favourable conditions for drying forest fuels.     

Re‐evaluation of the Optimal Operating Conditions for the Primary End of an Integrated Steel Plant using Multi‐objective Genetic Algorithms and Nash Equilibrium

Some existing work on optimizing the operational cost of the primary end of an integrated steel plant containing two blast furnaces utilizing both pellets and sinters, an electric furnace and a basic oxygen furnace was further advanced using a multi‐objective genetic algorithm, along with a Nash equilibrium analysis. The new formulation was able to improve the earlier results very significantly, suggesting the efficacy of the multi‐objective approach over the more conventional single objective genetic algorithms.     

Pharmacokinetics of cladribine in plasma and its 5''-monophosphate and 5''-triphosphate in leukemic cells of patients with chronic lymphocytic leukemia

PURPOSE: To determine whether microtubule- and actin-altering drugs, which have been shown to increase aqueous humor outflow, cause cellular contraction in human trabecular meshwork (HTM) cells. METHODS: HTM cells were plated in culture dishes containing a polymerized deformable silicone substrate. After 48 hours, the dishes were placed on an inverted microscope and treated with ethacrynic acid, colchicine, vinblastine, cytochalasin B, or 1-(5-isoquinolinylsulfonyl)-2-methylpiperazine (H-7) and then recorded on videotape for 15 minutes. An increase in silicone substrate wrinkle size and/or number indicated a contraction. Sham controls were used. RESULTS: Cellular contraction was observed with ethacrynic acid, colchicine, and vinblastine in the 10(-5) to 10(-4) M dosage range. Pretreatment with H-7 blocked these effects. Cytochalasin B did not produce cellular contraction. CONCLUSIONS: Microtubule disruption causes cellular contraction in HTM cells, and this effect depends on an intact actin cytoskeleton network. Contraction of trabecular meshwork cells in response to various stimuli is an attractive hypothesis for possible homeostatic mechanisms in the outflow pathway, and this may serve as a focus for novel glaucoma drug development.     

Variation in cyclic oxidation testing practice and data: The European situation before COTEST

A survey of existing testing practice and pre‐existing data was conducted to provide a starting point for the COTEST project on cyclic oxidation testing. The main parameters within the test that need to be controlled were identified as: control of test environment; temperature stability during hold periods; heating and cooling rates; specimen preparation; and post test evaluation. Existing experimental facilities were surveyed to establish the full range of variability within these parameters.     

On the release of glutamate and aspartate in the basal ganglia of the rat: interactions with monoamines and neuropeptides

Experiments were designed to determine the in vivo cell-cycle phase of lymphocytes in secondary lymphoid follicles, and whether B-cell proliferation and apoptosis occur within follicular dendritic cell (FDC)-associated clusters. Using frozen serial sections of human tonsils, lymphoid follicles were stained to reveal histone H3 mRNA, as an S-phase marker, using in situ hybridization, and stained immunohistochemically with antibodies against cyclin E as a late G1 phase marker, cyclin B1 and p34cdc2 as S-G2-M phase markers, and Ki-67 as a marker of cycling cells. Each LF was divided into five zones: mantle zone, outer zone, apical light zone, basal light zone and dark zone, with the help of haematoxylin and eosin staining, and a CD23 immunostain. The rate of occurrence of positively labelled cells was calculated by dividing the number of positive cells by the number of all cells in each zone. The cells that were positive for cyclin E, histone H3 mRNA, cyclin B1, p34cdc2, and Ki-67 were found most frequently in the dark zone (54.5 +/- 6.6%, 22.0 +/- 5.7%, 36.7 +/- 14.5%, 40.0 +/- 10.2%, and 59.0 +/- 13.4%, respectively), followed by the outer zone (52.7 +/- 7.8%, 14.9 +/- 4.1%, 22.9 +/- 9.7%, 24.9 +/- 7.9%, and 44.6 +/- 12.3%, respectively), showing that both the outer zone and the dark zone contain many proliferating lymphocytes. Furthermore, FDC-associated clusters and free lymphocytes were obtained from enucleated germinal centres, using enzymatic digestion. The rates of occurrence of cells that were positive for cyclin B1 and Ki-67 within the clusters (7.2 +/- 1.9% and 37.9 +/- 10.5% respectively) were significantly lower than those of free lymphocytes outside the clusters (22.2 +/- 4.0% and 62.8 +/- 14.0%, respectively). The rates of occurrence of apoptotic bodies and cells within the clusters, as detected by in situ tailing or in situ nick translation (0.2 +/- 0.4% and 0.4 +/- 0.4%, respectively) were significantly lower than those outside the clusters (1.1 +/- 0.3, 1.6 +/- 0.5%, respectively). These results suggest that FDC-associated clusters are not the site of proliferation, and that they rarely contain apoptotic bodies and cells of B lymphocytes.     

Carbon pricing and the diffusion of renewable power generation in Eastern Europe: A linear programming approach

The purpose of this paper is to analyze the costs for reducing CO₂ emissions in the power-generating sectors in Croatia, the European part of Russia, Macedonia, Serbia and the Ukraine in 2020 by using a linear programming model. The model takes into account the impact of technology learning and is based on the underlying assumptions of the so-called RAINS model frequently used to assess the potential and the costs for reducing air pollution in Europe. The results based on an exogenously given 15 percent reduction target for CO₂ emissions show that the marginal cost for switching from a carbon-intense fuel to either a low-carbon or to a renewable energy source differs significantly among the countries. The marginal costs range from 4 to 90€ per ton CO₂, and are mainly due to country differences in the availability of renewables, existing technologies and costs. The results also indicate that although it is clear that the Eastern European countries are not homogeneous in terms of CO₂ abatement potential and costs, no general conclusions can be made of the region. This may have important implications for future JI/CDM activities. For instance, risk factors such as policy uncertainty and institutional obstacles may become crucial in determining the future allocation of JI/CDM projects across the region.