Effect of temperature and branching on the nature and stability of alkene cracking intermediates in H-ZSM-5

Catalytic cracking of alkenes takes place at elevated temperatures in the order of 773–833 K. In this work, the nature of the reactive intermediates at typical reaction conditions is studied in H-ZSM-5 using a complementary set of modeling tools. Ab initio static and molecular dynamics simulations are performed on different C4single bond C5 alkene cracking intermediates to identify the reactive species in terms of temperature. At 323 K, the prevalent intermediates are linear alkoxides, alkene π-complexes and tertiary carbenium ions. At a typical cracking temperature of 773 K, however, both secondary and tertiary alkoxides are unlikely to exist in the zeolite channels. Instead, more stable carbenium ion intermediates are found. Branched tertiary carbenium ions are very stable, while linear carbenium ions are predicted to be metastable at high temperature. Our findings confirm that carbenium ions, rather than alkoxides, are reactive intermediates in catalytic alkene cracking at 773 K

Does the Use of Imported Intermediates Increase Productivity? Plant-Level Evidence

This paper examines whether importing intermediate goods improves plant performance. While addressing the issue of simultaneity of a productivity shock and decisions to import intermediates, we estimate the impact of the use of foreign intermediates on plants' productivity using plant-level Chilean manufacturing panel data. We found that the switching from being a non-importer to being an importer of foreign intermediates can improve productivity by 3.4 to 22.5 percentproductivity, imported intermediates, plant-level

Confirming the existence of π-allyl-palladium intermediates during the reaction of meta photocycloadducts with palladium(ii) compounds

The transient existence of π-allyl-palladium intermediates formed by the reaction of Pd(OAc)2 and anisole-derived meta photocycloadducts has been demonstrated using NMR techniques. The intermediates tended to be short-lived and underwent rapid reductive elimination of palladium metal to form allylic acetates, however this degradation process could be delayed by changing the reaction solvent from acetonitrile to chloroform

Eine Panel-Analyse des chinesischen Intraindustriellen Handels im Investitionsgütersektor

This paper adopts the Hausman-Taylor 2SLS error components approach in estimating the determinants of China's Intra-Industry Trade (IIT) in the capital goods sector with its 26 partner countries. It disaggregates IIT into horizontal IIT (HIIT) and vertical IIT (VIIT). Capital goods final products and intermediates are separately estimated in order to reveal the differentiated trade patterns. It finds that economic similarity is very significantly negatively correlated with the intermediates IIT, but to a less extent correlated with the final products IIT. Factor endowment is of no significance in determining IIT in the intermediates, although it is significantly positively correlated with the final products IIT. Economic size is significantly negatively correlated with both final products and intermediates IIT. Distance is not yet dead in impacting the level of final products IIT, but of less importance in influencing the intermediates IIT. China is exchanging intermediates in a less intraindustry manner with ASEAN nations. However, because VIIT is dominating TIIT, no significant differences exist between the estimation results of TIIT and VIIT.intra-industry trade, panel econometrics

Confirming the existence of π-allyl-palladium intermediates during the reaction of meta photocycloadducts with palladium(ii) compounds

The transient existence of π-allyl-palladium intermediates formed by the reaction of Pd(OAc)2 and anisole-derived meta photocycloadducts has been demonstrated using NMR techniques. The intermediates tended to be short-lived and underwent rapid reductive elimination of palladium metal to form allylic acetates, however this degradation process could be delayed by changing the reaction solvent from acetonitrile to chloroform

Total syntheses of conformationally-locked difluorinated pentopyranose analogues and a pentopyranosyl phosphate mimetic

Trifluoroethanol has been elaborated, via a telescoped sequence involving a metalated difluoroenol, a difluoroallylic alcohol, [2,3]-Wittig rearrangement, and ultimately an RCM reaction and requiring minimal intermediate purification, to a number of cyclooctenone intermediates. Epoxidation of these intermediates followed by transannular ring opening or dihydroxylation, then transannular hemiacetalization delivers novel bicyclic analogues of pentopyranoses, which were elaborated (in one case) to an analogue of a glycosyl phosphate

Characterization of Translocation Contact Sites Involved in the Import of Mitochondrial Proteins

Import of proteins into the mitochondrial matrix requires translocation across two membranes. Translocational intermediates of mitochondrial proteins, which span the outer and inner membrane simultaneously and thus suggest that translocation occurs in one step, have recently been described (Schleyer, M., and W. Neupert, 1985, Cell, 43:339-350). In this study we present evidence that distinct membrane areas are involved in the translocation process. Mitochondria that had lost most of their outer membrane by digitonin treatment (mitoplasts) still had the ability to import proteins. Import depended on proteinaceous structures of the residual outer membrane and on a factor that is located between the outer and inner membranes and that could be extracted with detergent plus salt. Translocational intermediates, which had been preformed before fractionation, remained with the mitoplasts under conditions where most of the outer membrane was subsequently removed. Submitochondrial vesicles were isolated in which translocational intermediates were enriched. Immunocytochemical studies also suggested that the translocational intermediates are located in areas where outer and inner membranes are in close proximity. We conclude that the membrane-potential-dependent import of precursor proteins involves translocation contact sites where the two membranes are closely apposed and are linked in a stable manner

Getting more than a fair share: nutrition of worker larvae related to social parasitism in the Cape honey bee Apis mellifera capensis

Besides activation of ovaries and thelytokous reproduction of Cape workers, larval nutrition is an important aspect in parasitism of the African honey bee. When reared by workers of other subspecies, Cape larvae receive more food which is slightly more royal jelly-like. This results in worker-queen intermediates, with reduced pollen combs, enlarged spermathecae and higher numbers of ovarioles. The intermediates weigh more and develop faster than normal workers. The appearance of worker-queen intermediates probably affects parasitism of the African honey bee colonies by Cape workers. Different levels of larval nutrition resulting in less distinct caste differentiation may be important for the reproductive success of Cape workers in their own colonies. Similar processes, albeit less pronounced, may occur in colonies of other subspecies

Effects of preconditioning and extrusion of linseed on the ruminal biohydrogenation of fatty acids 1. In vivo studies

The extent and intermediates of ruminal biohydrogenation (BH) of fatty acids (FA) from a blend of linseed and wheat bran (70:30) were investigated in the rumen fluid, rumen particle phase and duodenal flow. The blend was ground through a 3 mm screen and used raw or extruded, or was ground through a 6 mm screen and preconditioned. Three dry Holstein cows fitted with ruminal and duodenal cannulas were used in a 3 × 3 Latin square design, with 18 days adaptation. The diet contained 20% (DM basis) of the linseed based blend. Twelve samples taken over 3 days were composited for analysis of rumen fluid, rumen particle phase and duodenal flow. The BH of FA from linseed resulted in the appearance of a great number of C18:1 intermediates, among which trans-10+11 to trans-16C18:1 were the most abundant. The proportion of cis-9,trans-11C18:2 was low. Preconditioning coarsely ground linseed resulted in a lower extent of C18:2 and C18:3 BH, and lower proportions of trans-12 to trans-16C18:1 intermediates than extrusion or a lack of processing of finely ground linseed. On the contrary, extrusion did not affect the extent of BH and had no significant effect on the proportions of trans-C18:1 intermediates, but increased the proportion of cis-9,trans-11C18:2 in both rumen phases. Different digesta types resulted in different estimates of BH. The extent of BH and the proportions of trans-C18:1 intermediates were lower in the rumen particle phase and higher in the rumen fluid than in the duodenum. Moreover, interactions between digesta type and treatment of linseed were observed

Towards the conversion of carbohydrate biomass feedstocks to biofuels via hydroxylmethylfurfural

This review appraises the chemical conversion processes recently reported for the production of hydroxylmethylfurfural (HMF), a key biorefining intermediate, from carbohydrate biomass feedstocks. Catalytic sites or groups required for the efficient and selective conversion of hexose substrates to HMF are examined. The principle of concerted catalysis was used to rationalise the dehydration of fructose and glucose to HMF in non-aqueous media. A survey of reported reaction routes to diesel-range biofuel intermediates from HMF or furfural is presented and self-condensation reaction routes for linking two or more HMF and furfural units together toward obtaining kerosene and diesel-range biofuel intermediates are highlighted. The reaction routes include: benzoin condensation, condensation of furfuryl alcohols, hetero Diels–Alder reaction and ketonisation reaction. These reaction routes are yet to be exploited despite their potential for obtaining kerosene and diesel-range biofuel intermediates exclusively from furfural or hydroxylmethylfurfural