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Residue fluid catalytic cracking (RFCC) is a process that cracks heavy oil into light oil, such as gasoline, with zeolite catalysts. Treated atmospheric residue (AR) [low-sulfur bunker-C from the residue [...]

Background: Japanese hop is an important cause of weed pollinosis in East Asia. Its pollen is abundant in autumn. This pollen is known to be the cause of many allergic diseases. However, molecular characteristics of its allergens have not been elucidated. Objective: In this study, we produced recombinant proteins of allergen homologues from Japanese hop by the analysis of expressed sequence tags (EST), and evaluated its allergenicity. Methods: cDNA library was constructed using as little as 50 ng of total RNA from Japanese hop pollen. Allergen homologues were identified by the initial screening of 963 EST clones. Recombinant proteins were overexpressed in the E. coli expression system and purified using Ni-nitrilotriacetic acid-agarose. Purified proteins were analyzed by ELISA. Results and Discussion: Japanese hop pathogenesis-related 1 protein (PR-1) shares 37.0 to 44.4% of amino acid sequence identity with Art v 2, Cuc m 3, and Cyn d 24. Pectin methyl esterase (PME) shows 23.2 to 50.2% of identities to Act d 7, Ole e 11, and Sal k 1. Polygalacturonase (PGs) shows 16.7 to 19.3% of identities to Phl p 13, Cry j 2, Cha o 2, Jun a 2, Pla a 2, and Pla or 2. IgE antibodies from Japanese hop allergy patients’ sera recognized PR-1 (3.4%), PME (13.8%), PGs (3.7%), and profilin (13.8%), respectively. Conclusion: Novel allergenic components were identified, even though low IgE reactivity was displayed reflecting the low degree of cross-reactivity with other pollen allergens. We believe that these molecules have worth further studies.

Photophysics tunability through alteration of framework aperture (metal–organic framework (MOF) = variable; guest = constant) was probed for the first time in comparison with previously explored concepts (MOF = constant; guest = variable). In particular, analysis of the confinement effect on a photophysical response of integrated 5-(3-chlorobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (Cl-BI) chromophore allowed us to establish a photophysics–aperture relationship. To shed light on the observed correlation, the framework confined environment was replicated using a molecular cage, Pd6(TPT)4(TPT = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine), thus allowing for utilization of crystallography, spectroscopy, and theoretical simulations to reveal the effect a confined space has on the chromophore’s molecular conformation (including disruption of strong hydrogen bonding and novel conformer formation) and any associated changes on a photophysical response. Furthermore, the chosen Cl-oHBI@Pd6(TPT)4(Cl-oHBI = 5-(5-chloro-2-hydroxybenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one, chromophore) system was applied as a tool for targeted cargo delivery of a chromophore to the confined space of DNA, which resulted in promotion of chromophore–DNA interactions through a well-established intercalation mechanism. Moreover, the developed principles were applied toward utilizing a HBI-based chromophore as a fluorescent probe on the example of macrophage cells. For the first time, suppression of non-radiative decay pathways of a chromophore was tested by anchoring the chromophore to a framework metal node, portending a potential avenue to develop an alternative to natural biomarkers. Overall, these studies are among the first attempts to demonstrate the unrevealed potential of a confined scaffold environment for tailoring a material’s photophysical response.

Reaction of [(η⁵-C10H9)Mn(CO)3] (1) with L produced [(η³-C10H9)Mn(CO)3L] (2, L = P(OMe)3; 5, L = CO) in high yields. X-ray structural analysis of 2 confirmed an η³-bonding mode of the 1-hydronaphthalene ring. Thermal treatment of 2 led to [(η⁵-C10H9)Mn(CO)2P(OMe)3] (3). The η⁵-1-hydronaphthalene ring in 1 is quite easily ring-slipped, η⁵ ↔ η³. A kinetic study of the reaction of 1 with P(OMe)3 indicates that formation of 2 is first order in 1 and first order in P(OMe)3 with the following activation parameters:  ΔH^&thermod; = 6.9 ± 0.4 kcal/mol; ΔS^&thermod; = −32.6 ± 1.5 eu. Quantitative comparison between the reactivity of the indenyl complex [(η⁵-C9H7)Mn(CO)3] with P(OEt)3 and 1 with P(OMe)3 at 130 °C shows that the rate constant for 1 is 2 × 10⁶ times faster than that of the indenyl complex. The tremendous rate enhancement in 1 was rationalized as a stabilization of 2 by the second benzene ring. The facile ring-slippage in 1 has been utilized in the synthesis of [(η⁶-C10H8)Mn(CO)2P(OMe)3]BF4 and in the catalytic hydrosilylation of ketones. Complex 1 is an effective catalyst for the hydrosilylation of alkyl and aryl ketones with Ph2SiH2 as a silane source. The indenyl complex [(η⁵-C9H7)Mn(CO)3] has no catalytic activity in the hydrosilylation of ketones. The facile ring-slippage in the η⁵-1-hydronaphthalene ring plays a crucial role in the chemistry of 1.

RuCl3·3H2O complexes have been incorporated into polycarbonate using solvent. The interactions between Ru complexes and polycarbonate (PC) are examined by infrared spectroscopy and thermal analysis. The reaction chemistries of these Ru-containing films have been investigated by reacting the Ru sites with CO, O2, H2, D2, NO, and C2H4. They show interesting catalytic activities in various gas phase reactions under relatively mild conditions such as NO reduction, hydrogenation of ethylene and benzene, water-gas shift reaction, and oxidation of n-butyl sulfide.

From results of 1H NMR studies and stopped‐flow kinetics at a variety of temp. and the use of 18O‐labeled compounds the mechanisms of the title reactions are interpreted as initial attack by the Ru=O group of the oxidant (I).