Clean seeding for flow visualization and velocimetry measurements

Flow visualization, particle image velocimetry (PIV), and laser Doppler velocimetry (LDV) are among the most useful tools available for experimental aerodynamics studies. Implementation of these techniques, however, requires that seed material be introduced into the flow. The undesirable qualities of the seeding material often prevent the use of flow visualization and velocimetry techniques in many test environments. This is particularly true for large-scale, closed-circuit tunnels where facility operators must weigh the risks of facility contamination, sensor damage, and safety concerns that might result from the introduction of seed particles. Identification of a practical clean seeding material that minimizes or eliminates these concerns would enable flow visualization and velocimetry techniques to be deployed in these facilities. Here, we demonstrate two seeding systems that have the potential to provide such a solution. The first system is a new concept which uses liquid carbon dioxide that can be made to form discrete particles as it expands from a high-pressure tank. PIV measurements are demonstrated in several flows, including supersonic and subsonic tunnels, using these residue-free seed particles. The second system utilizes a combination of steam and liquid nitrogen to produce an aerosol or fog that serves as flow seeding. Water- or steam-based seeding has been previously demonstrated for flow visualization in subsonic tunnels; here however, we utilize this seed material for PIV and LDV measurements as well as for flow visualization in a large supersonic tunnel.     

Intrinsic broad-band white-light emission by a tuned, corrugated metal-organic framework

Herein we report on the broad-band direct white-light originating from a single component emitter, namely a novel three-periodic metal-organic framework (MOF). This material features an unprecedented topology with (3,4)-connected nodes. The structure-function relationship in this system is driven by two complementary unique structural features: corrugation and interpenetration. Good correlation between simulated and experimental emission spectra has been attained, resulting in optimized color properties that approach requirements for solid-state lighting (SSL). Guided by the optimized calculated spectra, the tunability of the assembly was proven by the successful in-framework co-doping of Eu(3+). This resulted in significantly improved color properties, opening new paths for the rational design of alternative materials for SSL applications.     

Mechanism for activation of triosephosphate isomerase by phosphite dianion: the role of a hydrophobic clamp

The role of the hydrophobic side chains of Ile-172 and Leu-232 in catalysis of the reversible isomerization of R-glyceraldehyde 3-phosphate (GAP) to dihydroxyacetone phosphate (DHAP) by triosephosphate isomerase (TIM) from Trypanosoma brucei brucei (Tbb) has been investigated. The I172A and L232A mutations result in 100- and 6-fold decreases in k(cat)/K(m) for the isomerization reaction, respectively. The effect of the mutations on the product distributions for the catalyzed reactions of GAP and of [1-(13)C]-glycolaldehyde ([1-(13)C]-GA) in D(2)O is reported. The 40% yield of DHAP from wild-type Tbb TIM-catalyzed isomerization of GAP with intramolecular transfer of hydrogen is found to decrease to 13% and to 4%, respectively, for the reactions catalyzed by the I172A and L232A mutants. Likewise, the 13% yield of [2-(13)C]-GA from isomerization of [1-(13)C]-GA in D(2)O is found to decrease to 2% and to 1%, respectively, for the reactions catalyzed by the I172A and L232A mutants. The decrease in the yield of the product of intramolecular transfer of hydrogen is consistent with a repositioning of groups at the active site that favors transfer of the substrate-derived hydrogen to the protein or the oxygen anion of the bound intermediate. The I172A and L232A mutations result in (a) a >10-fold decrease (I172A) and a 17-fold increase (L232A) in the second-order rate constant for the TIM-catalyzed reaction of [1-(13)C]-GA in D(2)O, (b) a 170-fold decrease (I172A) and 25-fold increase (L232A) in the third-order rate constant for phosphite dianion (HPO(3)(2-)) activation of the TIM-catalyzed reaction of GA in D(2)O, and (c) a 1.5-fold decrease (I172A) and a larger 16-fold decrease (L232A) in K(d) for activation of TIM by HPO(3)(2-) in D(2)O. The effects of the I172A mutation on the kinetic parameters for the wild-type TIM-catalyzed reactions of the whole substrate and substrate pieces are consistent with a decrease in the basicity of the carboxylate side chain of Glu-167 for the mutant enzyme. The data provide striking evidence that the L232A mutation leads to a ca. 1.7 kcal/mol stabilization of a catalytically active loop-closed form of TIM (E(C)) relative to an inactive open form (E(O)).     

Regioselective reduction of 3-substituted N-acylpyrazinium salts toward the synthesis of 1,2-dihydropyrazines

The regioselective reduction of 3-substituted N-acylpyrazinium salts with n-Bu(3)SnH has been developed for the synthesis of 3-substituted 1,2-dihydropyrazines in yields of 56-94%. Substitution of the pyrazinium salts with electron-donating groups favors the formation of the 1,2-isomers as a result of their better stability over the 1,6-isomers. Under mild acidic conditions, 3-methoxy substituted 1,2-dihydropyrazine was easily hydrolyzed in excellent yield to Δ(5)-2-oxopiperazine.     

From lin-benzoguanines to lin-benzohypoxanthines as ligands for Zymomonas mobilis tRNA-guanine transglycosylase: replacement of protein-ligand hydrogen bonding by importing water clusters

The foodborne illness shigellosis is caused by Shigella bacteria that secrete the highly cytotoxic Shiga toxin, which is also formed by the closely related enterohemorrhagic Escherichia coli (EHEC). It has been shown that tRNA-guanine transglycosylase (TGT) is essential for the pathogenicity of Shigella flexneri. Herein, the molecular recognition properties of a guanine binding pocket in Zymomonas mobilis TGT are investigated with a series of lin-benzohypoxanthine- and lin-benzoguanine-based inhibitors that bear substituents to occupy either the ribose-33 or the ribose-34 pocket. The three inhibitor scaffolds differ by the substituent at C(6) being H, NH(2), or NH-alkyl. These differences lead to major changes in the inhibition constants, pK(a) values, and binding modes. Compared to the lin-benzoguanines, with an exocyclic NH(2) at C(6), the lin-benzohypoxanthines without an exocyclic NH(2) group have a weaker affinity as several ionic protein-ligand hydrogen bonds are lost. X-ray cocrystal structure analysis reveals that a new water cluster is imported into the space vacated by the lacking NH(2) group and by a conformational shift of the side chain of catalytic Asp102. In the presence of an N-alkyl group at C(6) in lin-benzoguanine ligands, this water cluster is largely maintained but replacement of one of the water molecules in the cluster leads to a substantial loss in binding affinity. This study provides new insight into the role of water clusters at enzyme active sites and their challenging substitution by ligand parts, a topic of general interest in contemporary structure-based drug design.     

Impacts of earmarked private donations for disaster fundraising

Faced with large humanitarian emergencies like the earthquakes in Haiti and Japan, aid agencies have to decide how to collect money for their relief work. They can either decide to establish a special fund for the emergency and allow for earmarked donations or they can only allow for unearmarked donations. In this paper, we analyze impacts of this decision on donors, aid agencies, and policy makers. To this end, we compare two prevalent fundraising modes using optimization models: fundraising with the option of earmarking donations and fundraising without an earmarking option. In the earmarked case, we consider a new fundraising challenge, excessive funds raised for certain disaster relief projects. We find that desirable fundraising modes for donors, aid agencies, and policy makers differ depending on levels of several parameters, including an aid agency’s utility of a dollar raised, the fundraising cost factor, and donors’ unit utility of donations. Allowing for earmarking leads to a lower overall fundraising cost percentage. For emergencies with strong media attention and donor interest, allowing for earmarking of donations is likely to reduce fundraising activities of organizations with low fundraising costs, while it is likely to encourage fundraising activities among organizations with high fundraising costs.     

Quality assessment of a formulated Chinese herbal decoction, Kaixinsan, by using rapid resolution liquid chromatography coupled with mass spectrometry: A chemical evaluation of different historical formulae

Kaixinsan is an ancient Chinese herbal decoction mainly prescribed for patients suffering from mental depression. This decoction was created by Sun Si-miao of Tang Dynasty (A.D. 600) in ancient China, and was composed of four herbs: Radix and Rhizome Ginseng, Radix Polygalae, Rhizoma Acori Tatarinowii and Poria. Historically, this decoction has three different formulations, each recorded at a different point in time. In this study, the chemical compositions of all three Kaixinsan formulae were analyzed. By using rapid resolution LC coupled with a diode-array detector and an ESI triple quadrupole tandem MS (QQQ-MS/MS), the Radix and Rhizome Ginseng-derived ginsenosides including Rb(1), Rd, Re, Rg(1), the Radix Polygalae-derived 3,6'-disinapoyl sucrose, the Rhizoma Acori Tatarinowii-derived α- and β-asarone and the Poria-derived pachymic acid were compared among the three different formulations. The results showed variations in the solubility of different chemicals between one formula and the others. This systematic method developed could be used for the quality assessment of this herbal decoction.     

Alternative supply chain production-sales policies for new product diffusion: An agent-based modeling and simulation approach

Applying agent-based modeling and simulation (ABMS) methodology, this paper analyzes the impact of alternative production-sales policies on the diffusion of a new generic product and the generated NPV of profit. The key features of the ABMS model, that captures the marketplace as a complex adaptive system, are: (i) supply chain capacity is constrained; (ii) consumers’ new product adoption decisions are influenced by marketing activities as well as positive and negative word-of-mouth (WOM) between consumers; (iii) interactions among consumers taking place in the context of their social network are captured at the individual level; and (iv) the new product adoption process is adaptive. Conducting over 1 million simulation experiments, we determined the “best” production-sales policies under various parameter combinations based on the NPV of profit generated over the diffusion process. The key findings are as follows: (1) on average, the build-up policy with delayed marketing is the preferred policy in the case of only positive WOM as well as the case of positive and negative WOM. This policy provides the highest expected NPV of profit on average and it also performs very smoothly with respect to changes in build-up periods. (2) It is critical to consider the significant impact of negative word-of-mouth in choosing production-sales policies. Neglecting the effect of negative word-of-mouth can lead to poor policy recommendations, incorrect conclusions concerning the impact of operational parameters on the policy choice, and suboptimal choice of build-up periods.