Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Understanding heterogeneous catalysis on an atomic scale: a combined surface science and reactivity investigation for the dehydrogenation of ethylbenzene over iron oxide catalysts

In order to study the dehydrogenation of ethylbenzene to styrene, epitaxial iron oxide model catalyst films with Fe₃O₄(111), -Fe₂O₃(0001) and KFe _x O _y (111) stoichiometry were prepared in single crystal quality on Pt(111). They were investigated using surface science techniques before and after atmospheric pressure reaction experiments in a newly designed single crystal flow reactor. As expected from low-pressure measurements, Fe₃O₄(111) is catalytically inactive. The catalytic activity of -Fe₂O₃(0001) starts after an activation period of about 45 min. After that, the surface is essentially clean but shows a high concentration of defects. On the potassium-promoted films, however, the activation period is much longer, the activity then is higher and the surface gets covered completely with carbon and oxygen during reaction. This indicates a different reaction pathway on the promoted films with a carbon–oxygen species as catalytically active species.     

Synthesis and properties of copolymers from diphenylacetylene having a hexaphenylbenzene moiety

Summary Copolymerization of diphenylacetylene having a hexaphenylbenzene group, 1-[p-(pentaphenyl)phenyl]-2-phenylacetylene (1), with a few other diphenylacetylene derivatives (i.e., diphenylacetylene, 1-phenyl-2-[p-(trimethylsilyl)phenyl] acetylene, 1-phenyl-2-[p-n-octylphenyl]acetylene, (2a–c, respectively) and properties of the formed copolymers were investigated. No polymer was obtained in homopolymerization of 1 with TaCl₅-n-Bu₄Sn catalyst owing to steric hindrance. On the other hand, copolymerization with 2a–c proceeded at various feed ratios to give copolymers in moderate yields. Copoly(1/2a) (feed ratio 25/75) was soluble in toluene and CHCl₃ and its weight-average molecular weight (M _w) was ca. 31×10⁴ and relatively high. Copoly(1/2b) and copoly(1/2c) (both feed ratios 5/95) were soluble in common organic solvents, and had a large M _w up to ca. 1×10⁶. These copolymers were yellow to orange solids. Oxidative cyclodehydrogenation of hexaphenylbenzene groups in copoly(1/2a) was attempted in order to convert them into more conjugated groups. Received: 24 January 2000/Accepted: 17 February 2000     

In situ generation and screening of a dynamic combinatorial carbohydrate library against concanavalin A

Dynamic combinatorial chemistry (DCC) is a recently introduced approach that is based on the generation of combinatorial libraries by reversible interconversion of the library constituents. In this study, the implementation of such libraries on carbohydrate-lectin interactions was examined. The dynamic carbohydrate libraries were generated from a small set (four or six compounds) of initial carbohydrate dimers through mild disulfide interchange, and selection was performed under two conditions defining either adaptive or pre-equilibrated libraries. Upon initiation, libraries were formed that contained comparable amounts of 10 or 21 individual dimeric species, dynamically interchanging during the scrambling process. They were probed with respect to binding to the plant lectin concanavalin A, either present during library generation or added after equilibration. The libraries could be generated easily both in the presence and absence of the receptor, and a bis-mannose structure was preferentially bound and selected from the mixture. Scrambling of the library in the presence of the receptor resulted in slightly higher yields than when the receptor was added after scrambling, indicating that the receptor to some extent acts as a thermodynamic trap during library generation. The present results illustrate the extention of the DCC approach to carbohydrate recognition groups, the generation of isoenergetic dynamic libraries, and the implementation of either adaptive or pre-equilibrated procedures.     

Enzymatic modification of the functional, nutritional and sensorial properties of soybeans for special feeding

Production of new protein-based products for special nutrition such as hypoallergenic infant formulas, fortified beverages and nutraceutics, require ideal ingredients. Protein ingredients were developed by enzymatic hydrolysis and methionine synthesis of soy protein. Hydrolysis was done at 4% (w/v) using porcine pancreatic enzymes (4% w/w), 50 degrees C, 6 h and pH 8. After drying powder was resuspended (20% w/v) and incubated with 7.6% (w/w) methionine methyl-ester, 1% (w/w) chymotrypsin and 3 M glycerol, 37 degrees C, 3 h and pH 7. Hydrolysates were fractionated by ultrafiltration (UF) before and after enrichment (E): FI > 10, 10 > FII > 3 and 3 > FIII > 1 kDa. Functional properties, amino acid content, anti-physiological factor activities and antigenicity were assayed for all the UF fractions and the soybean meal. Protein quality bioassay and sensorial test of an non-enriched fraction and an enriched fraction were performed. Functional properties were positively modified by hydrolysis and synthesis by using a minimum time and methionine added for the last reaction. After UF all the fractions under 10 kDa showed 100% solubility (pH 4 and 7), good clarity, acceptable foam capacity and negligible antigenicity and antiphysiological activities. Additionally, methionine enrichment enhanced their nutritional value, upgrading sulfur amino acid requirements for infants and adults. Because functionality and nutritional value FIII-E could be used for hypoallergenic infant formulas, FII-E for fortified soluble formulas and nutraceutics and FI-E for a semi-solid baby food.     

Flow patterns and oil—water dispersion in a 0.38 m diameter oscillatory baffled column

We report our experimental flow visualization observations of flow patterns and experimental oil‐water dispersion measurements in an oscillatory baffled column (OBC) of an internal diameter 380 mm. Both types of experiments were carried out covering an identical range of oscillation frequencies, amplitudes, orifice diameters and baffle spacings. The flow visualization observations show that eddy mixing has been achieved in the pilot OBC and the intensity of which is largely dependent on the operational and geometrical parameters tested, which is similar to that in a smaller scale OBC. The scale‐up correlation was found to be linear. The oil‐water dispersion measurements show that the degree of the dispersion depends significantly on the oscillation frequency and amplitude with an increase in either leading to an increase in dispersion. The effect of the orifice diameter on the oil—water dispersion is also evident, but the effect of the baffle spacing is much weaker. Based on the experimental data we have established a correlation relating the degree of oil—water dispersion to the power input to the system. We have also compared the power requirement to achieve a complete dispersion in the pilot OBC with that in a bench scale OBC of 50 mm diameter and found that the energy dissipation is more economical in the large scale application.     

The nature of the active phase of the Fe/K-catalyst for dehydrogenation of ethylbenzene

The industrial catalyst for high temperature dehydrogenation of ethylbenzene based on iron and potassium oxides undergoes, under reaction conditions, essentially a transformation into magnetite, Fe₃O₄, and a mixture of ternary oxides containing trivalent iron, viz. K₂Fe₂₂O₃₄ and KFeO₂. The latter compound constitutes the outside of the catalyst particles and is indeed the catalytically active phase.     

Polymerization of isoprene in n-heptane with triethylaluminum–titanium tetrachloride catalyst. I. Effect of Al/Ti ratio on stereoregularity,conversion, molecular weight,and molecular weight distribution

The influence of the Al/Ti ratio of the heterogeneous Ziegler–Natta catalyst system AlEt₃–TiCl₄ on the isoprene polymerization in n-heptane at 30°C in a bench scale reactor was investigated. Each batch run consisted of 50 mL isoprene, 200 mL n-heptane with 0.45 and 0.5g catalyst. Conversion of isoprene and molecular weights of polyisoprene increased with increasing Al/Ti ratio, reaching their maxima values at 1.0 and 1.2, respectively. Conversion and molecular weights decreased remarkably at a higher ratio of Al/Ti. As this ratio decreases from the value of 1.2 to 0.4, the cis1,4 content in polyisoprene decreased from 97 to 25%. When the ratio of Al/Ti increased from 1.2 to 2.2 the cis-1,4 structure of polyisoprene decreased from 97 to 85%.     

The speed of sound and isentropic bulk modulus of biodiesel at 21°C from atmospheric pressure to 35 MPa

Biodiesel, an alternative diesel fuel consisting of the alkyl monoesters of fatty acids from vegetable oils and animal fats, can be used in existing diesel engines without modification. However, property changes associated with the differences in chemical structure between biodiesel and petroleumbased diesel fuel may change the engine's injection timing. These injection timing changes can change the exhaust emissions and performance from the optimized settings chosen by the engine manufacturer. This study presents the results of measurements of the speed of sound and the isentropic bulk modulus for methyl and ethyl esters of fatty acids from soybean oil and compares them with No. 1 and No. 2 diesel fuel. Data are presented at 21±1°C and for pressures from atmospheric to 34.74 MPa. The results indicate that the speed of sound and bulk modulus of the monoesters of soybean oil are higher than those for diesel fuel and these can cause changes in the fuel injection timing of diesel engines. Linear equations were used to fit the data as a function of pressure, and the correlation constants are given.     

Cleavable surfactants

Cleavable surfactants are of interest for several reasons. Above all, the development of surfactants with weak bonds deliberately built into the structure is driven by the need for improved biodegradability of amphiphiles. The breakdown may be catalyzed by enzymes, and biodegradation would be the normal mechanism in sewage plants. Alternatively, the surfactant may degrade by chemical means, e.g., induced by acid, alkali, ultraviolet (UV) light, heat, or ozone. Acid- and alkali-labile surfactants have attracted particular attention, and there is often a compromise between required stability at one stage and ease of breakdown at a subsequent stage. The paper reviews the main routes used to prepare cleavable surfactants and points out advantages and disadvantages of the different approaches. Emphasis is placed on the development during recent years. Cyclic and acyclic acetals, ketals, and ortho esters are the most important types of bonds for the preparation of acid-labile surfactants, whereas alkali-labile amphiphiles usually are based on ester bonds. The ester bond approach has been particularly important for cationic surfactants, and so-called ester quats have rapidly taken a large share of the traditional market for quats. Betaine esters constitute a special class of ester with very pronounced pH dependence. UV-labile surfactants based, for instance, on an azo bond, offer promise for the future.