Vibrational frequencies associated with the inter-stitial carbon atoms in the large metal cluster complexes (NMe4)2[Os10C(CO)24] and H2Os10C(CO)24

Determination of the vibrational frequencies of the interstitial carbon atoms in the metal clusters [Os₁₀C(CO)₂₄]^2? and H₂Os₁₀C(CO)₂₄, confirmed in the latter by ¹³C enrichment, shows that the protonated cluster species exhibits considerable deviation from pseudo-cubic symmetry in the crystal, in contrast to the dianion.     

Cooperation between scientists and the government in the US: benefits and problems

This paper discusses the importance of maintaining close working relations between scientists and their government. Several examples of this cooperation in the U.S. are presented to illustrate the benefits, as well as problems, that result from such cooperation, or lack thereof. These examples include government support of scientific research, as well as contributions by science to help governments understand both the possibilities and the limitations of science as they formulate national policy.     

Many-body potential for point defect clusters in Fe-C alloys

Modeling the consequences of crystalline defects requires efficient interaction sampling. Empirical potentials can identify relevant pathways if the energetics and configurations of competing defects are captured. Here, we develop such a potential for an alloy of arbitrary point defect concentration, body-centered cubic alpha-Fe supersaturated in C. This potential successfully calculates energetically favored defects, and predicts formation energies and configurations of multicarbon-multivacancy clusters that were not attainable with existing potentials or identified previously via ab initio methods.     

Structural basis for the exceptional stability of bisaminoacylated nucleotides and transfer RNAs

At least one bisaminoacyl-tRNA is synthesized in nature (by Thermus thermophilus phenylalanyl-tRNA synthetase), and many disubstituted tRNAs have been prepared in vitro. Such misacylated tRNAs are able to participate in protein synthesis, even though they lack the free 2'-OH group of the 3'-terminal adenosine moiety. Their ready participation in protein synthesis implies significant chemical reactivity. The basis for this reactivity has been documented previously. Surprisingly, the aminoacyl moieties of these tRNAs also exhibit exceptional chemical stability. In the present report, bisaminoacylated nucleotides are investigated computationally and experimentally to define the basis for the stability of such species. Molecular modeling of bisalanyl-AMP in the absence of solvent and in the presence of a limited number of water molecules revealed two common features among the low-energy structures. The first was the presence of H-bonding interactions between the two aminoacyl moieties. The second was the presence of a H-bonding interaction between the 2'-O-alanyl moiety and the N-3 atom of the adenine nucleobase, typically mediated through a water molecule. The prediction of an interaction between an aminoacyl moiety and the adenine nucleobase was confirmed experimentally by comparing the behavior of bisalanyl-AMP and bisalanyl-UMP in the presence of model nucleophiles. This study suggests a possible role for the adenosine moiety at the 3'-end of aminoanyl-tRNAs in controlling the stability and reactivity of the aminoacyl moiety and has important implications for the reactivity and stability of normal aminoacyl-tRNAs.     

Extremal dependence analysis of network sessions

We refine a stimulating study by Sarvotham et al. (Comput Networks 48:335–350, 2005) which highlighted the influence of peak transmission rate on network burstiness. From TCP packet headers, we amalgamate packets into sessions where each session is characterized by a 5-tuple (S,D,R,R ^∨,Γ)=(total payload, duration, average transmission rate, peak transmission rate, initiation time). After careful consideration, a new definition of peak rate is required. Unlike Sarvotham et al. (Comput Networks 48:335–350, 2005) who segmented sessions into two groups labelled alpha and beta, we segment into 10 sessions according to the empirical quantiles of the peak rate variable as a demonstration that the beta group is far from homogeneous. Our more refined segmentation reveals additional structure that is missed by segmentation into two groups. In each segment, we study the dependence structure of (S,D,R) and find that it varies across the groups. Furthermore, within each segment, session initiation times are well approximated by a Poisson process whereas this property does not hold for the data set taken as a whole. Therefore, we conclude that the peak rate level is important for understanding structure and for constructing accurate simulations of data in the wild. We outline a simple method of simulating network traffic based on our findings.     

Radiochemical Feasibility of Mixing of 99mTc-MAA and 90Y-Microspheres with Omnipaque Contrast

Yttrium-90 (⁹⁰Y) microspheres are widely used for the treatment of liver-dominant malignant tumors. They are infused via catheter into the hepatic artery branches supplying the tumor under fluoroscopic guidance based on pre-therapy angiography and Technetium-99m macroaggregated albumin (^99mTc-MAA) planning. However, at present, these microspheres are suspended in radiolucent media such as dextrose 5% (D5) solution. In order to monitor the real-time implantation of the microspheres into the tumor, the ⁹⁰Y microspheres could be suspended in omnipaque contrast for allowing visualization of the correct distribution of the microspheres into the tumor. The radiochemical purity of mixing ⁹⁰Y-microspheres in various concentrations of omnipaque was investigated. The radiochemical purity and feasibility of mixing ^99mTc-MAA with various concentrations of a standard contrast agent were also investigated. Results showed the radiochemical feasibility of mixing ⁹⁰Y-microspheres with omnipaque is radiochemically acceptable for allowing real-time visualization of radioembolization under fluoroscopy.     

Effects of Silk Fibroin Enzyme Hydrolysates on Memory and Learning: A Review

Silk protein products have been used for a wide range of applications. This review focuses on the studies conducted relative to cognitive functions with silk fibroin enzyme hydrolysates (FEH) in humans and animals. All known studies reported in PubMed and Google Scholar have been included. Studies have been conducted on children, high school and college students, adults and seniors, ranging in ages from 7–92 years. Doses of 200–600 mg silk FEH per day for three weeks to 16 weeks have been used. Based on these studies, it can be concluded that silk FEH exhibit beneficial cognitive effects with respect to memory and learning, attention, mental focus, accuracy, memory recall, and overall memory and concentration. These conclusions are supported by studies in rats and mice. Mechanistic studies that have been conducted in animals and cell culture systems are also reviewed. These studies indicate that silk FEH exerts its positive effects on memory and learning by providing neuroprotection via a complex mechanism involving its potent antioxidant and inflammation-inhibiting activities. Acetylcholine (ACh) is secreted by cholinergic neurons, and plays a role in encoding new information. Silk FEH were shown to decrease the levels of the pro-oxidant and pro-inflammatory mediators interlukin-1 (IL-1β), IL-6 and tumor necrosis factor-alpha (TNF-α), protecting the cholinergic system from oxidative stress, thus enhancing ACh levels in the brain, which is known to promote cognitive functions. In addition, the expression of brain-derived neurotrophic factor (BNDF), which is involved in the survival of neurons, is enhanced, and an increase in the expression of the phosphorylated cAMP response element-binding protein (p-CREB) occurs, which is known to play a positive role in cognitive functions. No adverse effects have been reported in association with the use of silk FEH.     

The very low-pressure dehydrogenation of cis-2-butene. The activation energy for 1,4-H2 elimination

Pyrolysis of cis-butene-2 under conditions of very low pressure (VLPP) has been studied in the range of 1100–1300°K. The principal products are butadiene and H₂, obtained in a unimolecular reaction. A competing reaction to form butene-l accounts for from 10% to 40% of the overall decomposition over the range. Using a «tight» model for the transition state and RRKM theory yields a high-pressure, unimolecular rate constant for the 1,4-H₂ elimination of where θ = 2.303RT in kcal/mol. There is some surface reaction of butadiene at these temperatures to yield H₂ + nonvolatile residue. Butene-l proceeds to decompose irreversibly to allyl + methyl radicals which have been observed directly. Comparison with related reactions leads to the conclusion that orbital symmetry-forbidden, 1,2-H₂ elimination from saturated organic compounds will have activation energies too high to observe.