Effect of syngas addition on lower alkene production by the oxidative cracking of hexane

The lower alkene production by the gas-phase oxidative cracking (GOC) or catalytic oxidative cracking (COC) of hexane (C6) with added syngas was investigated. The addition of syngas to the COC process could effectively enhance the selectivity to lower alkenes and decrease the selectivity to COx, because of the preferential reaction between O-2 with H-2 contained in the syngas, whereas it has little effect on the conversion of C6 and product distribution in the GOC process. The high selectivity to lower alkenes of 70% and low selectivity to CO, of 6% at C6 conversion of 66% were achieved over 0.1% Pt/MgAl2O4 catalyst. The COC process of C6 combined with the syngas in the feed could directly produce a gas mixture of lower alkenes, H-2, and CO, which usually is a suitable feedstock for the hydroformylation process.

Rapid protein identification using monolithic enzymatic microreactor and LC-ESI-MS/MS

A monolithic enzymatic microreactor was prepared in a fused-silica capillary by in situ polymerization of acrylamide, glycidyl methacrylate (GMA) and ethylene dimethacrylate (EDMA) in the presence of a binary porogenic mixture of dodecanol and cyclohexanol, followed by ammonia solution treatment, glutaraldehyde activation and trypsin modification. The choice of acrylamide as co-monomer was found useful to improve the efficiency of trypsin modification, thus, to increase the enzyme activity. The optimized microreactor offered very low back pressure, enabling the fast digestion of proteins flowing through the reactor. The performance of the monolithic microreactor was demonstrated with the digestion of cytochrome c at high flow rate. The digests were then characterized by CE and HPLC-MS/MS with the sequence coverage of 57.7%. The digestion efficiency was found over 230 times as high as that of the conventional method. in addition, for the first time, protein digestion carried out in a mixture of water and ACN was compared with the conventional aqueous reaction using MS/MS detection, and the former solution was found more compatible and more efficient for protein digestion.

Differences in growth and nitrogen productivity between a stay-green genotype and a wild-type of Lolium perenne under limiting relative addition rates of nitrate supply

James Macduff, Neil Raistrick and Mervyn Humphreys (2002). Differences in growth and nitrogen productivity between a stay-green genotype and a wild-type of Lolium perenne under limiting relative addition rates of nitrate supply. Physiologia Plantarum, 116 (1), 52-61. Sponsorship: BBSRC RAE2008

Barnacle cement: a polymerization model based on evolutionary concepts.

Enzymes and biochemical mechanisms essential to survival are under extreme selective pressure and are highly conserved through evolutionary time. We applied this evolutionary concept to barnacle cement polymerization, a process critical to barnacle fitness that involves aggregation and cross-linking of proteins. The biochemical mechanisms of cement polymerization remain largely unknown. We hypothesized that this process is biochemically similar to blood clotting, a critical physiological response that is also based on aggregation and cross-linking of proteins. Like key elements of vertebrate and invertebrate blood clotting, barnacle cement polymerization was shown to involve proteolytic activation of enzymes and structural precursors, transglutaminase cross-linking and assembly of fibrous proteins. Proteolytic activation of structural proteins maximizes the potential for bonding interactions with other proteins and with the surface. Transglutaminase cross-linking reinforces cement integrity. Remarkably, epitopes and sequences homologous to bovine trypsin and human transglutaminase were identified in barnacle cement with tandem mass spectrometry and/or western blotting. Akin to blood clotting, the peptides generated during proteolytic activation functioned as signal molecules, linking a molecular level event (protein aggregation) to a behavioral response (barnacle larval settlement). Our results draw attention to a highly conserved protein polymerization mechanism and shed light on a long-standing biochemical puzzle. We suggest that barnacle cement polymerization is a specialized form of wound healing. The polymerization mechanism common between barnacle cement and blood may be a theme for many marine animal glues.

Direct Carbon-Carbon Bond Formation via Reductive Soft Enolization: A Kinetically Controlled syn-Aldol Addition of alpha-Halo Thioesters and Enolizable Aldehydes

The direct addition of enolizable aldehydes and a-halo thioesters to produce beta-hydroxy thioesters enabled by reductive soft enolization is reported. The transformation is operationally simple and efficient and has the unusual feature of giving high syn-selectivity, which is the opposite of that produced for (thio)esters under conventional conditions. Moreover, excellent diastereoselectivity results when a chiral nonracemic alpha-hydroxy aldehyde derivative is used.

Does an incremental filling technique reduce polymerization shrinkage stresses

It is widely accepted that volumetric contraction and solidification during the polymerization process of restorative composites in combination with bonding to the hard tissue result in stress transfer and inward deformation of the cavity walls of the restored tooth. Deformation of the walls decreases the size of the cavity during the filling process. This fact has a profound influence on the assumption-raised and discussed in this paper-that an incremental filling technique reduces the stress effect of composite shrinkage on the tooth. Developing stress fields for different incremental filling techniques are simulated in a numerical analysis. The analysis shows that, in a restoration with a well-established bond to the tooth-as is generally desired-incremental filling techniques increase the deformation of the restored tooth. The increase is caused by the incremental deformation of the preparation, which effectively decreases the total amount of composite needed to fill the cavity. This leads to a higher-stressed tooth-composite structure. The study also shows that the assessment of intercuspal distance measurements as well as simplifications based on generalization of the shrinkage stress state cannot be sufficient to characterize the effect of polymerization shrinkage in a tooth-restoration complex. Incremental filling methods may need to be retained for reasons such as densification, adaptation, thoroughness of cure, and bond formation. However, it is very difficult to prove that incrementalization needs to be retained because of the abatement of shrinkage effects.

Effect of 0.5 wt % Cu addition in Sn–3.5% Ag solder on the dissolution rate of Cu metallization

The dissolution of thin film under-bump-metallization (UBM) by molten solder has been one of the most serious processing problems in electronic packaging technology. Due to a higher melting temperature and a greater Sn content, a molten lead-free solder such as eutectic SnAg has a faster dissolution rate of thin film UBM than the eutectic SnPb. The work presented in this paper focuses on the role of 0.5 wt % Cu in the base Sn–3.5%Ag solder to reduce the dissolution of the Cu bond pad in ball grid array applications. We found that after 0.5 wt % Cu addition, the rate of dissolution of Cu in the molten Sn–3.5%Ag solder slows down dramatically. Systematic experimental work was carried out to understand the dissolution behavior of Cu by the molten Sn–3.5%Ag and Sn–3.5%Ag–0.5%Cu solders at 230–250 °C, for different time periods ranging from 1 to 10 min. From the curves of consumed Cu thickness, it was concluded that 0.5 wt % Cu addition actually reduces the concentration gradient at the Cu metallization/molten solder interface which reduces the driving force of dissolution. During the dissolution, excess Cu was found to precipitate out due to heterogeneous nucleation and growth of Cu6Sn5 at the solder melt/oxide interface. In turn, more Cu can be dissolved again. This process continues with time and leads to more dissolution of Cu from the bond pad than the amount expected from the solubility limit, but it occurs at a slower rate for the molten Sn–3.5%Ag–0.5%Cu solder. © 2003 American Institute of Physics.