Coulomb effects in low energy fission

The structures in the total kinetic energy (TKE) distributions in cold fission of²³⁴U and²³⁶U are interpreted in terms of the Coulomb interaction energy (C) between fragments at the scission point. The maximal value ofC, C _max, corresponding to the most compact scission configuration, is calculated for several mass fragmentations. It is shown that withQ being constant,C _max increases if one increases the charge asymmetry for a given primary fragmentation. This condition produces oscillations with a period of approximately 5 amu ofC _max as a function of the light fragment mass which are correlated with the observed oscillations of the maximal value of TKE. Moreover, the enhancement of the yields of the more asymmetric charge fragmentation for a given fragmentation is explained.     

Development of a chemiluminescent ELISA and a colloidal gold-based LFIA for TNT detection

To identify the explosive used in a terrorist attack, or to obtain an early sign of environmental pollution it is important to use simple and rapid assays able to detect analytes at low levels, possibly on-site. This is particularly true for TNT (2,4,6-trinitrotoluene), one of the most employed explosives in the 20th century and at the same time, because of its toxicity, a well known pollutant. In this work we describe the development of an indirect competitive ELISA with chemiluminescent detection (CL-ELISA) and of a lateral-flow immunoassay (LFIA) based on colloidal gold nanoparticle labels. A commercially available monoclonal antibody was used and 13 specially synthesized conjugates were tested. We optimized the assay by determining the optimal concentration of monoclonal antibody and conjugates and the influence of various non-specific factors such as: tolerance to organic solvents at different concentrations, the washing and competitive step time, and the cross-reactivity with related compounds. The sensitivity and reproducibility of the CL-ELISA were good (LOD and IC₅₀ values in the ng mL⁻¹ range, and CV value about 7%). It has been applied to real samples of various materials involved in a controlled explosion of an “improvised explosive device”. Three extraction procedures were tested on these samples, all employing methanol as the solvent. The lateral flow immunoassay (LFIA), developed by using the same immunoreagents, reached a detection limit of 1 μg mL⁻¹ when tested on the same samples analysed by CL-ELISA.      

Aspects of electronic transport in YBaCo4O7+δ pellets

YBaCo₄O_7+δ powders were obtained by standard solid state reaction und their structural, morphological and electrical properties carefully analyzed. The X-ray powder diffraction patterns showed reflexes corresponding to a pure hexagonal structure (space group P6₃mc). The lattice parameters resulted to be very close to those reported in the literature for high-quality samples. Raman spectra at room temperature allowed for identifying bands associated with vibrating modes of CoO₄ and Y₂O₆ in tetrahedral and octahedral coordination, respectively. Additional bands, which seemed to stem from CoO in octahedral coordination, were also clearly identified. The dependence of the resistivity on temperature showed a semiconducting-like behavior and no indication of structural phase transition was observed up to temperatures as low as 20 K. The electronic transport mechanism in this material was analyzed within the framework of standard models as thermal activation, polaronic-type conductivity or Mott variable-range hopping. Contrary to some reports in the literature in which thermal activation was reported to be the main transport mechanism, careful analysis of the obtained resistivity data (this work) favored the variable-range hopping conduction model. Certainly, the experimental data recorded in a wide temperature range were well described by the function ρ(T) = ρ₀exp[(T^*/T)^1/4]. The fit procedure yielded a temperature scale T^* ～ 10⁶ K, similar to that found in other transition metal oxides. This parameter, in turn, allowed for estimating the density of states at the Fermi level N(E_F) for this compound.     

Branch-and-price approach for the multi-skill project scheduling problem

This work introduces a procedure to solve the multi-skill project scheduling problem (MSPSP) (Néron and Baptista, International symposium on combinatorial, optimization (CO’2002), 2002). The MSPSP mixes both the classical resource constrained project scheduling problem and the multi-purpose machine model. The aim is to find a schedule that minimizes the completion time (makespan) of a project, composed of a set of activities. In addition, precedence relations and resources constraints are considered. In this problem, resources are staff members that master several skills. Thus, a given number of workers must be assigned to perform each skill required by an activity. Practical applications include the construction of buildings, as well as production and software development planning. We present a column generation approach embedded within a branch-and-price (B&P) procedure that considers a given activity and time-based decomposition approach. Obtained results show that the proposed B&P procedure is able to reach optimal solutions for several small and medium sized instances in an acceptable computational time. Furthermore, some previously open instances were optimally solved.     

The corrections for non-ideal behavior of the epithermal neutron spectrum and the restitution of the simplicity in parametric activation analysis

The errors occurred when α, the parameter that accounts for the non-ideal behavior of the epithermal flux, are neglected, have been evaluated for the determination of twenty elements in biological materials, using. gold and sodium comparators, and zirconium to measure the thermal to epithermal flux ratio (f). Sodium allows the determination of 15 elements, and up to 18 elements can be determined in positions relatively well thermalized by the simultaneous use of gold and sodium comparators, in all the cases with errors ≦2%, when α is not considered. Results obtained for reference materials are presented.     

Imidazolinone herbicides in strongly acidic media: Speciation and electroreduction

From UV-visible measurements and potentiometric titrations it follows that the lowest pK values (pK₁) of imidazolinone herbicides correspond to the simultaneous protonation/dissociation equilibria of both the pyridinic (or quinolinic) nitrogen and the carboxyl group, the following pK (pK₂) to the imminium nitrogen and the basic pK (pK₃) to the dissociation of the imido nitrogen. Below pH 6 and down to pH c.a. 2.5, the dominant form of the herbicide is a double ion having both positive and negative charges, this being important in discussing the effect of pH in the natural dynamics of imidazolinone herbicides, especially in their soil sorption. Electrochemical studies of the reduction of the herbicides were made on mercury and carbon electrodes in strongly acidic media (0.1 to 2.7 M H₂SO₄) as well up to pH 7. The reduction signals were all attributed to the reduction of the imidazolinone ring except the second peak/wave that was found to have originated by the reduction of the pyridine/quinoline ring. A signal observed in strongly acidic media and at highly negative overpotentials was attributed to the reduction of the imidazolinone ring of the product of the previous reduction in a process consisting of two reversible electron transfers followed by a protonation reaction.     

Regioselective formation of N-alkyl-3,5-pyrazole derived ligands. A synthetic and computational study

New N-alkyl-3,5-pyrazole derived ligands were synthesized by reaction between 3,5-pyrazole derived ligands and the appropriate haloalkane in toluene or THF using NaOEt or NaH as base. When the precursor ligand bears a pyridyl substituent the alkylation reaction presents a large regioselectivity. Theoretical calculations have been carried out to rationalize the experimental observations. It has been shown that regioselectivity is governed by the formation of Na⁺-pyrazolide chelate complexes.     

Mechanistic investigations reveal that dibromobimane extrudes sulfur from biological sulfhydryl sources other than hydrogen sulfide

Hydrogen sulfide (H₂S) has emerged as an important biological signaling molecule in the last decade. During the growth of this field, significant controversy has arisen centered on the physiological concentrations of H₂S. Recently, a monobromobimane (mBB) method has been developed for the quantification of different biologically-relevant sulfide pools. Based on the prevalence of the mBB method for sulfide quantification, we expand on this method to report the use of dibromobimane (dBB) for sulfide quantification. Reaction of H₂S with dBB results in formation of highly-fluorescent bimane thioether (BTE), which is readily quantifiable by HPLC. Additionally, the reaction of sulfide with dBB to form BTE is significantly faster than the reaction of sulfide with mBB to form sulfide dibimane. Using the dBB method, BTE levels as low as 0.6 pM can be detected. Upon use of the dBB method in wild-type and CSE^–/– mice, however, dBB reports significantly higher sulfide levels than those measured using mBB. Further investigation revealed that dBB is able to extract sulfur from other sulfhydryl sources including thiols. Based on mechanistic studies, we demonstrate that dBB extracts sulfur from thiols with α- or β-hydrogens, thus leading to higher BTE formation than from sulfide alone. Taken together, the dBB method is a highly sensitive method for H₂S but is not compatible for use in studies in which other thiols are present.     

Simultaneous preference estimation and heterogeneity control for choice-based conjoint via support vector machines

Support vector machines (SVMs) have been successfully used to identify individuals’ preferences in conjoint analysis. One of the challenges of using SVMs in this context is to properly control for preference heterogeneity among individuals to construct robust partworths. In this work, we present a new technique that obtains all individual utility functions simultaneously in a single optimization problem based on three objectives: complexity reduction, model fit, and heterogeneity control. While complexity reduction and model fit are dealt using SVMs, heterogeneity is controlled by shrinking the individual-level partworths toward a population mean. The proposed approach is further extended to kernel-based machines, conferring flexibility to the model by allowing nonlinear utility functions. Experiments on simulated and real-world datasets show that the proposed approach in its linear form outperforms existing methods for choice-based conjoint analysis.     

Cardinal characteristics at κ in a small u(κ) model

We provide a model where $\mathfrak{u}(\kappa )<2^{\kappa }$ for a supercompact cardinal κ. [10] provides a sketch of how to obtain such a model by modifying the construction in [6]. We provide here a complete proof using a different modification of [6] and further study the values of other natural generalizations of classical cardinal characteristics in our model. For this purpose we generalize some standard facts that hold in the countable case as well as some classical forcing notions and their properties.