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

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

Prompt Formation of Organic Acids in Pulse Ozonation of Terpenes on Aqueous Surfaces

A major atmospheric process, the gas-phase ozonation of terpenes yields suites of products via a cascade of chemically activated intermediates that ranges from primary ozonides to dioxiranes. If a similar mechanism operated in water, as it is generally assumed, such intermediates would be deactivated within picoseconds and, henceforth, be unable to produce carboxylic acids in microseconds. Herein, we report the online electrospray mass spectrometric detection of (M + 2O – H^+) and (M + 3O – H^+) carboxylates on the surface of aqueous β-caryophyllene (C_(15)H_(24), M = 204 Da) microjets exposed to a few ppmv of O_3(g) for < 10 μs. Since neither species is formed on dry solvent microjets and both incorporate deuterium from D_2O, we infer that carboxylates ensue from the interaction of nascent intermediates with interfacial water via heretofore unreported processes. These interfacial events proceed much faster than those in bulk liquids saturated with ozone

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

Intermediates and Generic Convergence to Equilibria

Known graphical conditions for the generic or global convergence to equilibria of the dynamical system arising from a reaction network are shown to be invariant under the so-called successive removal of intermediates, a systematic procedure to simplify the network, making the graphical conditions easier to check.Comment: Added theorem 1 and corrected an error in the proof of theorem

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

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

Local content protection reconsidered: the case of domestic monopsonist

In this paper we examine how local content protection (LCP) affects the use of the domestic intermediates, the use of total intermediates and the domestic welfare when domestic intermediate-goods market is under monopsony. In the domestic intermediate-goods market under monopsony, the marginal expenditure cost (MEC) of using domestic intermediates has a discontinuous segment because the average expenditure cost (AEC) is a kinked curve. It is shown that there exists a case where because of the discontinuity of the marginal expenditure cost, LCP has no effect on the use of domestic intermediates and has a negative impact on the domestic final-goods producer. This paper provides a summary of the general effects of LCP on the domestic intermediate-goods market under monopsony in terms of resource allocations and the domestic welfare. Moreover, the effects of LCP under monopsony are compared with the case under perfect competition and under free trade.

Hydroxy terminated perfluoro ethers Patent

Chemical synthesis of hydroxy terminated perfluoro ethers as intermediates for highly fluorinated polyurethane resin

BLUF Domain Function Does Not Require a Metastable Radical Intermediate State

BLUF (blue light using flavin) domain proteins are an important family of blue light-sensing proteins which control a wide variety of functions in cells. The primary light-activated step in the BLUF domain is not yet established. A number of experimental and theoretical studies points to a role for photoinduced electron transfer (PET) between a highly conserved tyrosine and the flavin chromophore to form a radical intermediate state. Here we investigate the role of PET in three different BLUF proteins, using ultrafast broadband transient infrared spectroscopy. We characterize and identify infrared active marker modes for excited and ground state species and use them to record photochemical dynamics in the proteins. We also generate mutants which unambiguously show PET and, through isotope labeling of the protein and the chromophore, are able to assign modes characteristic of both flavin and protein radical states. We find that these radical intermediates are not observed in two of the three BLUF domains studied, casting doubt on the importance of the formation of a population of radical intermediates in the BLUF photocycle. Further, unnatural amino acid mutagenesis is used to replace the conserved tyrosine with fluorotyrosines, thus modifying the driving force for the proposed electron transfer reaction; the rate changes observed are also not consistent with a PET mechanism. Thus, while intermediates of PET reactions can be observed in BLUF proteins they are not correlated with photoactivity, suggesting that radical intermediates are not central to their operation. Alternative nonradical pathways including a keto–enol tautomerization induced by electronic excitation of the flavin ring are considered