Hydrogen Bond Compression during Triple Proton Transfer in Crystalline Pyrazoles. A Dynamic 15N NMR Study

Using dynamic solid state ¹⁵N CPMAS NMR spectroscopy (CP ≡ cross polarization, MAS ≡ magic-angle spinning), the kinetics of degenerate intermolecular triple proton and deuteron transfers in the cyclic trimers of ¹⁵N-labeled polycrystalline 4-nitropyrazole (4NO₂P) and 4-bromopyrazole (4BrP) have been studied as a function of temperature and are compared to the kinetics of triple proton transfer in bulk solid 3,5-dimethylpyrazole (DMP) studied previously. The results show that the transfer kinetics in the new trimers are much faster than in DMP. However, the kinetic HHH/HHD/HDD/DDD isotope effects of 4NO₂P are similar to those of DMP. These effects indicate a single barrier for the triple proton transfers where all three protons lose zero-point energy in the transition state, as expected for a structure with three compressed hydrogen bonds. At low temperatures, strong deviations from an Arrhenius-behavior are observed which are described in terms of a modified Bell tunneling model and a concerted proton motion. The barrier for the triple proton transfer in 4NO₂P and 4BrP is substantially smaller than in DMP. As there is no correlation with the electronic properties of the substituents, we assign this finding to steric effects where the bulky methyl groups of DMP in the 3- and 5-positions hinder the hydrogen bond compression, in contrast to 4NO₂P and 4BrP exhibiting substitutents in the 4-position. These results lead to a minimum energy pathway of the proton transfer following in the absence of steric hindering the hydrogen bond correlation line q₁ = f(q₂), established previously, where q₁ represents the deviation of the proton from the hydrogen bond center and q₂ the N…N distance. Tunneling occurs at constant N…N distances.     

Sugar-based surfactants for consumer products and technical applications

Sugar-based surfactants, such as sorbitan esters, sucrose esters, alkyl polyglycosides, and fatty acid glucamides gain increasing attention due to advantages with regard to performance, health of consumers, and environmental compatibility compared to some standard products. Sorbitan esters are well established products, which are mainly used as leather and textile auxiliaries or as emulsifiers for food at a volume of approx. 20,000 t/a. Sucrose esters are relatively hydrophobic products. The actual market size is estimated to be < 4,000 t/a – the main application being emulsifiers for food and cosmetics. Their use is still limited. Alkyl polyglycosides and fatty acid glucamides represent a perfect amphiphilic structure with excellent surface activity as well as solubility due to highly selective syntheses. For alkyl polyglycosides industrial processes have been developed in the past couple of years and a total capacity of ca. 80,000 t/a has been established. They are mainly used for cosmetic, manual dishwashing, and detergent applications. Fatty acid glucamides to date are exclusively used by one company in liquid and powdered detergents. The estimated production capacity is approx. 40,000 t/a. Comparable in their performance profile as co-surfactants, both products differ in their raw material base: whereas in the case of the fatty acid glucamides methylamine is incorporated in the product, alkyl polyglycosides are completely based on renewable resources. This, combined with very good performance and mildness, could be one reason why alkyl polyglycosides are the most successful sugar-based surfactants nowadays. Research to develop derivatives on this basis is still ongoing.     

Variability of particle number emissions from diesel and hybrid diesel-electric buses in real driving conditions

A linear mixed model was developed to quantify the variability of particle number emissions from transit buses tested in real-world driving conditions. Two conventional diesel buses and two hybrid diesel-electric buses were tested throughout 2004 under different aftertreatments, fuels, drivers, and bus routes. The mixed model controlled the confounding influence of factors inherent to on-board testing. Statistical tests showed that particle number emissions varied significantly according to the after treatment, bus route, driver, bus type, and daily temperature, with only minor variability attributable to differences between fuel types. The daily setup and operation of the sampling equipment (electrical low pressure impactor) and mini-dilution system contributed to 30-84% of the total random variability of particle measurements among tests with diesel oxidation catalysts. By controlling for the sampling day variability, the model better defined the differences in particle emissions among bus routes. In contrast, the low particle number emissions measured with diesel particle filters (decreased by over 99%) did not vary according to operating conditions or bus type but did vary substantially with ambient temperature.     

Mapping woody-biomass supply costs using forest inventory and competing industry data

The goals of energy independence and sustainability have motivated many countries to consider biomass-based energy sources. The United States has substantial and increasing forest resources that could be used to produce both electricity and liquid fuel. However, these forest resources are highly heterogeneous in terms of the wood’s properties, the logging cost, the spatial distribution, and the value to other industries. These factors make predicting costs and selecting plant locations particularly challenging. When dealing with forest biomass, feedstock cost and location have frequently been highly simplified in previous studies. This paper presents a methodology for combining highly resolved forest inventory and price data with records of competing industries to develop detailed maps of feedstock availability. The feedstock sourcing strategy of the proposed bioenergy plants is modeled by a cost-minimizing linear program, as is the feedstock selection of the competing mills. A case study is performed on the southeast United States.     

Greenhouse gas emissions from the international maritime transport of New Zealand's imports and exports

Greenhouse gas emissions from international maritime transport are exempt from liabilities under the Kyoto Protocol. Research into quantifying these emissions is ongoing, and influences policy proposals to reduce emissions. This paper presents a cargo-based analysis of fuel consumption and greenhouse gas emissions from New Zealand's international maritime transport of goods. Maritime transport moves 99.5% (by mass) of New Zealand's internationally traded products. It is estimated that 73% of visiting vessels' activity can be directly attributed to the movement of goods in and out of New Zealand. A cargo-based methodology was used to estimate that the international maritime transport of New Zealand's imports and exports consumed 2.5 million tonnes (Mt; 2.6 billion litres) of fuel during the year 2007, which generated 7.7 Mt of carbon dioxide (CO₂) emissions. Double-counting of emissions would occur if a similar method was applied to all New Zealand's trading partners. In contrast, since few large vessels refuel in New Zealand, the National Greenhouse Gas Inventory listed 2007 international maritime transportation emissions as 0.98 Mt of CO₂, calculated from fuel bunkered for international transport. The results, therefore, show a significant difference between activity-based and bunker-fuel methodologies in quantifying New Zealand's emissions. International policy implications are discussed.     

CuInS2-Poly(3-(ethyl-4-butanoate)thiophene) nanocomposite solar cells: Preparation by an in situ formation route, performance and stability issues

In this contribution we present an in situ method for the preparation of CuInS₂-poly(3-(ethyl-4-butanoate)thiophene) (P3EBT) nanocomposite layers and their application in nanocomposite solar cells. A precursor solution containing copper and indium salts, thiourea and the conjugated polymer was prepared in pyridine, which was coated onto glass/ITO substrates followed by a heating step at 180 °C. The heating step induced the formation of the CuInS₂ nanoparticles homogeneously dispersed in the conjugated polymer matrix. The formation of the nanocomposite was investigated in situ by X-ray scattering techniques and TEM methods showing that nano-scaled CuInS₂ was formed. By addition of small amounts of zinc salt to the precursor solution, zinc containing CuInS₂ (ZCIS) was formed. ZCIS-P3EBT active layers exhibited higher V_OC than CuInS₂-P3EBT layers and showed efficiencies of about 0.4%. Additionally the stability of the solar cells was tested over a time scale of 172 h.     

Modulation of bovine mononuclear cell proliferation during physiological transitions of the mammary gland

Mammary secretions and blood were collected from five primiparous Holstein cows 14 d following cessation of milking and 14 d prior to parturition for preparation of serum and mammary secretion skim fractions. Mammary secretions and blood were collected from the same animals 15 to 18 d following cessation of milking and 2 to 13 d prior to parturition for isolation of mononuclear cells. Effects of serum on mammary gland mononuclear cell proliferation and skim fractions from mammary secretions on blood mononuclear cell proliferation were evaluated. Mononuclear cell proliferation was evaluated in a mitogen-induced lymphocyte proliferation assay and in a mixed leukocyte assay. Proliferative responses of blood and mammary gland mononuclear cells did not vary significantly between the two time periods evaluated. Mammary secretion skim fractions obtained at both time periods significantly suppressed blood mononuclear cell proliferation. In contrast, exogenous serum enhanced mammary gland mononuclear cell proliferation in response to mitogens and allogeneic cells. Ability to enhance in vitro proliferation of mammary mononuclear cells isolated during physiological transitions of the mammary gland may suggest the potential for enhancing mammary mononuclear cell proliferation in vivo to reduce incidence of new intramammary infections at times when the mammary gland is highly susceptible.     

Parallel FTIR-ATR and gravimetrical in-situ measurements on sodium alanate powder samples during hydrogen desorption

An experimental set-up has been developed to carry out in-situ measurements on hydrogen storage materials. It has been used to perform FTIR–ATR measurements on sodium alanate samples during hydrogen desorption and, in parallel, to perform gravimetrical measurements on the same sample. The ATR spectra showed the typical broad Al–H vibrational features, changing according to the phase change the material undergoes during the load cycle. It is shown that the absorbance of the material at these bands and the hydrogen content correspond to each other in a reproducible way. This behavior may be used to measure the hydrogen mass released by an alanate hydrogen reservoir by measuring the optical absorbance at defined wavelengths. In this paper the results of these experiments that may give rise to the realization of a level sensor in future hydrogen storage applications are presented.     

Protective effect of Enterococcus faecium J96, a potential probiotic strain, on chicks infected with Salmonella Pullorum

Enterococcus faecium J96 was isolated from a healthy free-range chicken and it inhibited Salmonella Pullorum, in vitro, due to its lactic acid and bacteriocin production. In vivo assays were carried out with 30-h-old broiler chicks. The lactic acid bacteria (approximately 1 x 10(9) cells per chick) were orally administered as preventive and as therapeutic treatments. In the first case they were given to the chicks twice a day for 3 consecutive days. In the second case the lactic bacteria were administered in the same way after a 24-h challenge by Salmonella Pullorum (in both instances the salmonella dose was 1 x 10(5) cells per chick). Cecal contents, liver, and spleens were analyzed and liver and spleen fragments were also fixed in formaldehyde (pH 7.00) in order to determine salmonella translocation. The chickens that were preventively treated with E. faecium J96 survived the Salmonella Pullorum challenge. Those that were infected on the first day and then inoculated with lactic bacteria died 4 days later. Salmonellae were isolated from their livers and spleens. From these results we may conclude that E. faecium J96 can protect newly hatched chicks from Salmonella Pullorum infection but cannot act as a good therapeutic agent.