Early stages hydration of high initial strength Portland cement

Thermogravimetry (TG) and derivative thermogravimetry (DTG) were used to analyze the early stages of hydration of a high-initial strength and sulphate resistant Portland cement (HS SR PC) within the first 24 h of setting. The water/cement (W/C) mass ratios used to prepare the pastes were 0.35, 0.45, and 0.55. The hydration behavior of the pastes was analyzed through TG and DTG curves obtained after different hydration times on calcined cement mass basis to have a same composition basis to compare the data. The influence of the W/C ratio on the kinetics of the hydration process was done through the quantitative analysis of the combined water of the main hydration products formed in each case. TG and DTG curves data calculated on calcined mass basis of all the results were converted to initial cement mass basis to have an easier way to analyze the influence of the W/C ratio on the free and combined water of the different main hydrated phases. The gypsum content of the pastes was totally consumed in 8 h for all cases. A significant part of the hydration process occurs within the first 14 h of setting and at 24 h the highest hydration degree, indicated by the respective content of formed calcium hydroxide, occurs in the case of the highest initial water content of the paste.     

Comprehensive study of honey with protected denomination of origin and contribution to the enhancement of legal specifications

In this study the characterization of a total of 60 honey samples with Protected Denomination of Origin (PDO) collected over three harvests (2009-2011, inclusive), from the Northeast of Portugal was carried out based on the presence of pollen, physicochemical and microbiological characteristics. All samples were found to meet the European Legislation, but some didn't meet the requirements of the PDO specifications. Concerning the floral origin of honey, our results showed the prevalence of rosemary (Lavandula pedunculata) pollen. The microbiological quality of all the analyzed samples was satisfactory, since fecal coliforms, sulfite-reducing clostridia and Salmonella were absent, and molds and yeasts were detected in low counts. Significant differences between the results were studied using one-way analysis of variance (ANOVA), followed by Tukey's HSD test. The samples were submitted to discriminant function analysis, in order to determine which variables differentiate between two or more naturally occurring groups (Forward Stepwise Analysis). The variables selected were in this order: diastase activity, pH, reducing sugars, free acidity and HMF. The pollen spectrum has perfect discriminatory power. This is the first study in which a honey with PDO was tested, in order to assess its compliance with the PDO book of specifications.     

Preparation of Dry Extract of<em> Mikania glomerata</em> Sprengel (Guaco) and Determination of Its Coumarin Levels by Spectrophotometry and HPLC-UV

Guaco (Mikania glomerata Sprengel) syrup is one of the most popular herbal medicines used to treat the symptoms of asthmatic bronchitis, cough and hoarseness. The coumarin 2H-1-benzopyran-2-one, is one of the major constituents of Guaco and contributes to its pharmacological effects. The pharmaceutical capsule form of dry extract of Guaco is recommended by the Brazilian Program of Medicinal Plants and Herbal Medicines and used in primary health care. In order to identify a new protocol to obtain the raw material for Guaco capsule production we evaluated two methods, including a freeze-drying process (lyophilization) and the spray-dryer technique, as well as the use of two adjuvants, Maltodextrins and Aerosil^?, in different concentrations. The coumarin levels of the dried extracts were analyzed by UV-spectrophotometry and HPLC-UV/DAD. The adjuvant Aerosil^? 8% showed better dry powder physical appearance. Lyophilization was observed to be the best process to obtain the dry extract of Guaco based on the measured coumarin levels.     

Gold nanoparticle/charged silsesquioxane films immobilized onto Al/SiO2 surface applied on the electrooxidation of nitrite

In this work, gold nanoparticles lower than 10?nm were prepared in an aqueous medium using two charged silsesquioxanes, the propylpyridinium chloride and propyl-1-azonia-4-azabicyclo[2.2.2]octane chloride, as stabilizer agents which revealed to be water-soluble. This stabilization method is innovative allowing thin films containing gold nanoparticles to be obtained, and it was used for the first time in the preparation of carbon paste electrodes (CPEs). The charged silsesquioxanes were characterized by liquid ¹³C NMR. The gold nanoparticle/silsesquioxane systems were characterized by ultraviolet–visible spectroscopy (UV–Vis) and transmission electron microscopy. In sequence, they were immobilized on silica matrix coated with aluminum oxide. The resulting solid materials designated as Au-Py/AlSi and Au-Db/AlSi were characterized by infrared spectroscopy and N₂ adsorption/desorption isotherms. The results showed that the gold nanoparticle/silsesquioxane systems are strongly adhered to the surface-forming thin films. The Au-Py/AlSi and Au-Db/AlSi materials were used to prepare CPEs for the electrooxidation of nitrite (NO ₂ ^? ) using cyclic voltammetry and differential pulse voltammetry. The Au-Py/AlSi and Au-Db/AlSi CPEs showed high sensitivity and detection limits of 71.87 and 53.66?μA?mmol^–1?L and 1.3 and 3.0?μmol?L^–1, respectively.     

Nitroxyl radical self assembled monolayers: Ion pairing investigation in organic and aqueous media

Self assembled monolayers (SAMs) formed from TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) derivative thiols have been studied by electrochemical quartz crystal microbalance (EQCM) in both aqueous and non-aqueous solvents. The in situ study of the mass transport occurring during the oxidation of TEMPO provides evidence of a ion pair formation without incorporation of solvent in densely packed nitroxyl radical SAMs. For SAMs having a low nitroxyl radical surface coverage, the effect of mixed SAMs is evidenced and seems to avoid the solvent incorporation.     

Counting spectral radii of matrices with positive entries

The sum–product conjecture of Erd?s and Szemerédi states that, given a finite set A$A$ of positive numbers, one can find asymptotic lower bounds for max{|A+A|,|A⋅A|}$max\{|A+A|,|A\cdot A|\}$ of the order of |A|^1+δ${\left|A\right|}^{1+\delta }$ for every δ<1$\delta <1$. In this paper we consider the set of all spectral radii of n×n$n\times n$ matrices with entries in A$A$, and find lower bounds for the cardinality of this set. In the case n=2$n=2$, this cardinality is necessarily larger than max{|A+A|,|A⋅A|}$max\{|A+A|,|A\cdot A|\}$.     

Simple dynamic location problem with uncertainty: a primal-dual heuristic approach

Abstract

In this paper, the simple dynamic facility location problem is extended to uncertain realizations of the potential locations for facilities and the existence of customers as well as fixed and variable costs. With limited knowledge about the future, a finite and discrete set of scenarios is considered. The decisions to be made are where and when to locate the facilities, and how to assign the existing customers over the whole planning horizon and under each scenario, in order to minimize the expected total costs. Whilst assignment decisions can be scenario dependent, location decisions have to take into account all possible scenarios and cannot be changed according to each scenario in particular. We first propose a mixed linear programming formulation for this problem and then we present a primal-dual heuristic approach to solve it. The heuristic was tested over a set of randomly generated test problems. The computational results are provided.     

MPOC: an agglomerative algorithm for multicriteria partially ordered clustering

In the field of multicriteria decision aid, considerable attention has been paid to supervised classification problems where the purpose is to assign alternatives into predefined ordered classes. In these approaches, often referred to as sorting methods, it is usually assumed that classes are either known a priori or can be identified by the decision maker. On the other hand, when the objective is to identify groups (clusters) of alternatives sharing similar characteristics, the problem is known as a clustering problem, also called an unsupervised learning problem. This paper proposes an agglomerative clustering method based on a crisp outranking relation. The method regroups alternatives into partially ordered classes, based on a quality of partition measure which reflects the percentage of pairs of alternatives that are compatible with a decision-maker’s multicriteria preference model.     

Structural control of the electronic properties of photodynamic azobenzene-derivatized pi-conjugated oligothiophenes

Quaterthiophenes containing a median 3,3'-dimethoxybithiophene (4MTZ) or bis(3,4-ethylenedioxythiophene) (4ETZ) block and an azobenzene group attached at two internal beta-positions of the end thiophene rings have been synthesized. The analysis of the crystal structure of the two compounds by X-ray diffraction shows that, for 4MTZ, the quaterthiophene chain adopts a syn-anti-syn conformation similar to the parent system based on unsubstituted quaterthiophene. In contrast, 4ETZ presents an all-anti conformation stabilized by noncovalent intramolecular interactions between oxygen atoms and thiophenic sulfur atoms. The effect of the photoisomerization of the azobenzene group on the electronic properties of the attached pi-conjugated quaterthiophene chain has been analyzed by UV-vis spectroscopy and cyclic voltammetry. The results obtained for 4MTZ suggest very limited geometrical changes due to the restricted rotation around the central interannular single bond caused by steric interactions between the methoxy groups. In contrast, upon trans to cis photoisomerization of the attached azobenzene group of 4ETZ, the quaterthiophene chain undergoes a reversible conformational switch to a final state with a lower HOMO level and a larger HOMO-LUMO gap than the initial state.     

Synthesis and reactivity of uranium(IV) amide complexes supported by a triamidotriazacyclononane ligand

Reaction of [U{(SiMe2NPh)3-tacn}Cl] with LiNEt2 or LiNPh2 affords the corresponding amide compounds, [U{(SiMe2NPh)3-tacn}(NR2)] (R = Et (1), R = Ph (2)). The complexes have been fully characterized by spectroscopic methods and the solid-state structure of 1 was determined by single-crystal X-ray diffraction analysis. The six nitrogen atoms of the tris(dimethylsilylanilide)triazacyclononane ligand are in a trigonal prismatic configuration with the nitrogen atom of the diethylamide ligand capping one of the trigonal faces of the trigonal prism. Crystallization of 2 from CH3CN solution gave crystals of the six-membered heterocycle [U{(SiMe2NPh)3-tacn}{kappa2-(HNC(Me))2CC[triple bond]N}] (3). The reactivity of the amides was investigated. Both compounds undergo acid-base reactions with protic substrates such as HOC6H2-2,4,6-Me3, 3,5-Me2pzH (pz = pyrazolyl) and HSC5H4N to give the corresponding [U{(SiMe2NPh)3-tacn}X] (X = OC6H2-2,4,6-Me3 (4), 3,5-Me2pzH (5), kappa2-SC5H4N (6)) complexes. The solid-state structures of and were determined by single-crystal X-ray diffraction and revealed that the compounds are eight-coordinate with dodecahedral geometry.