Kinetics of hydantoin formation

The reaction of lignite in a slagging gasifier produces reactants which in turn form 5,5-dimethylhydantoin (DMH) as a major constituent in the condensate water. Variations in plant operating conditions made it impossible to accurately study the kinetics of formation of DMH in the actual gasifier water, and thus a model system was chosen. The reaction of acetone cyanohydrin in the presence of excess ammonium carbonate at concentrations approaching those obtained in the condensate water were studied at 50,70, and 90 °C. Secondorder kinetics were obeyed, and the pseudo second-order rate constants at the respective temperatures were 1.86, 3.6, and 4.62 dm³ mol^{? 1} h^{? 1}. Independent variation of the concentration of either acetone, cyanide, ammonia or carbonate gave results consistent with the interpretation that the formation of DMH is first order in all reactants: rate of formation of DMH = k[acetone][HCN][NH₃][CO₂]. The pseudo second-order rate constant is a complex rate constant including several rapid equilibria. A mechanism consistent with the kinetic data is presented.     

Conformational Molecular Switches for Post-CMOS Nanoelectronics

Theoretical treatments forecast that bistable CMOS devices using electronic charge as a state variable will operate at their maximum thermal dissipation limit possibly as early as 2012. The problem is further compounded by increasing manufacturing challenges associated with the ever decreasing logic switch dimensions. These challenges require the development of new fabrication strategies that replace or complement current top-down lithography with bottom-up protocols using controlled self-assembly of nanomaterial building blocks. To answer some of these issues, this paper focuses on a new device paradigm consisting of an arene-metal-arene conformational switch, addressable through capacitive, inductive, or resonant-tunneling field coupling. The operating principle is based on voltage-tunable modulation in quantum electron transmission. The switch is open (off) when the metal ion is displaced to a position at a C-H bond on the arene ring due to an externally applied bias. Conversely, when the external bias is removed, the metal ion moves to an axis- symmetric position on the arene ring, and the switch is closed (on). The paper presents a summary of the architecture, operating principle, and advantages of the conformational switch, along with associated findings from proof-of-concept theoretical and experimental studies of its target specifications and performance. The paper also discusses opportunities and challenges related to the integration of conformational switches into hybrid CMOS-molecular and monolithic (all molecular) circuits.     

Ensuring primary realization of pressure unit in the vacuum range without typically utilized static expansion system

After the break-up of Czechoslovakia in 1993 the primary metrological standards authority almost fully remained in Slovakia. So we had to build our primary vacuum metrology anew. But we could do it using uptodate techniques that are more effective and they enable us to fulfil our task more effectively and in a shorter time.The steady demand to widen the lower pressure range and a steady demand for maximal accuracy collide with the financial possibilities open to a small country. So it is impossible to follow the classical pattern for the vacuum standards: liquid columns, static expansion system and dynamic expansion system. But it is possible to utilize contemporary progress in construction of piston manometers. This enables us to discard liquid column and static expansion techniques in favour of piston technique [Tesar J, Prazak D. Vacuum 2002; 67: 311, Tesar J, Prazak D, Krajicek Z. In:Proceedings of international symposium on Pressure and Vacuum, 2003. p. 169, Tesar J, Repa P, Prazak D, Krajicek Z, Peksa L. Vacuum 2004; 76: 491.]. Such system fulfils all the needs of a little industrial country and is economically acceptable.     

A multivariate classification of individual household census data for Italy

Never before have regional scientists had access to individual census data for an entire country. The paper describes the application of a taxonomic procedure to classify the 15.6 million households identified by the 1971 Italian census. The results are important both for what they reveal about Italian social structure and because they provide a basis for a constructing aggregate census data so that within area variations are retained.     

Catalyst instabilities during the liquid phase partial oxidation of methane

A promising catalytic system for the low temperature oxidation of methane to a methanol derivative has been investigated under both batch and semi-continuous operation in two different reactor types. The system comprises of a bimetallic palladium and copper(II) chloride catalyst contained in a trifluoroacetic acid (TFA) and an aqueous phase. Methane, oxygen and a co-reductant carbon monoxide constitute the gas phase. Typical operating conditions were a temperature of 85 °C and a pressure of 83 bar.

The yields of the methyl trifluoroacetate product observed in this present work were less than those obtained in other batch autoclave works, which employed only 4 ml of liquid phase, compared with 50 ml in this study. Furthermore, an encouraging initial product formation rate of ca. 40 mol/m³ h, quickly decreased after the first hour, and came to an apparent end after only 2 h. This observation had not been reported previously.

Work performed in a semi-continuous porous tube reactor (300 ml of re-circulating liquid phase) also showed the same reaction characteristics as in the batch reactor. Thus, the deteriorating product formation rate cannot be attributed to gaseous reactant depletion (batch operation). The results suggest problems associated with catalyst instabilities, e.g. with the previously elucidated Wacker chemistry.     

Testability-analysis driven test-generation of analogue cores

A new definition of the testability transfer factor for circuit components that provides better sensitivity with respect to parametric deviations is presented. New equations for the testability measures in a mixed-signal core are given. Testability analysis is used for test-pattern generation and for consideration of inserting wrapper cells. The simulation results show the effectiveness of the approach.     

Plasma viral RNA load predicts disease progression in accelerated feline immunodeficiency virus infection

Viral RNA load has been shown to indicate disease stage and predict the rapidity of disease progression in human immunodeficiency virus type 1 (HIV-1)-infected individuals. We had previously demonstrated that feline immunodeficiency virus (FIV) RNA levels in plasma correlate with disease stage in infected cats. Here we expand upon those observations by demonstrating that plasma virus load is 1 to 2 logs higher in cats with rapidly progressive FIV disease than in long-term survivors. Differences in plasma FIV RNA levels are evident by 1 to 2 weeks after infection and are consistent throughout infection. We also evaluated humoral immune responses in FIV-infected cats for correlation with survival times. Total anti-FIV antibody titers did not differ between cats with rapidly progressive FIV disease and long-term survivors. These findings indicate that virus replication plays an important role in FIV disease progression, as it does in HIV-1 disease progression. The parallels in virus loads and disease progressions between HIV-1 and FIV support the idea that the accelerated disease model is well suited for the study of therapeutic agents directed at reducing lentiviral replication.     

Analysis of Interconnected Oscillators by Dissipativity Theory

This paper employs dissipativity theory for the global analysis of limit cycles in particular dynamical systems of possibly high dimension. Oscillators are regarded as open systems that satisfy a particular dissipation inequality. It is shown that this characterization has implications for the global stability analysis of limit cycle oscillations: i) in isolated oscillators, ii) in interconnections of oscillators, and iii) for the global synchrony analysis in interconnections of identical oscillators     

HotSpot: a compact thermal modeling methodology for early-stage VLSI design

This paper presents HotSpot-a modeling methodology for developing compact thermal models based on the popular stacked-layer packaging scheme in modern very large-scale integration systems. In addition to modeling silicon and packaging layers, HotSpot includes a high-level on-chip interconnect self-heating power and thermal model such that the thermal impacts on interconnects can also be considered during early design stages. The HotSpot compact thermal modeling approach is especially well suited for preregister transfer level (RTL) and presynthesis thermal analysis and is able to provide detailed static and transient temperature information across the die and the package, as it is also computationally efficient.     

A comparison of the dissolution of model compounds and the kerogen of Green River oil shale by oxidation with perchloric acid — A model for the kerogen of Green River oil shale

A stepwise degradation of a kerogen concentrate of Green River oil shale was effected by oxidation with perchloric acid of varying boiling point and concentration. Dissolution of the kerogen concentrate occurred between 160 and 170°C. Several model compounds were also oxidized with perchloric acid. The model compounds were polyethylene, graphite, nylon, and polyethylene oxide. The results indicated that the kerogen was similar to polyethylene oxide. The results of this study and previous work were used to present a model for the structure of the kerogen of Green River oil shale.