Simultaneous measurements of heat of hydration and chemical shrinkage on hardening cement pastes

Isothermal calorimetry and chemical shrinkage measurements are two independent techniques used to study the development of hydration in cementitious systems. In this study, calorimetry and chemical shrinkage measurements were combined and simultaneously performed on hydrating cement paste samples. Portland cement pastes with different water to cement ratios and a cement paste containing calcium sulfoaluminate clinker and anhydrite were studied. The combined calorimetry/chemical shrinkage test showed good reproducibility and revealed the different hydration behavior of sealed samples and open samples, i.e., samples exposed to external water during hydration. Large differences between sealed and open samples were observed in a Portland cement paste with low water to cement ratio and in the calcium sulfoaluminate paste; these effects are attributed to self-desiccation of the sealed pastes. Once the setup is fully automatized, it is expected that combined calorimetry/chemical shrinkage measurements can be routinely used for investigating cement hydration.     

Millimeter-scale contact printing of aqueous solutions using a stamp made out of paper and tape

This communication describes a simple method for printing aqueous solutions with millimeter-scale patterns on a variety of substrates using an easily fabricated, paper-based microfluidic device (a paper-based "stamp") as a contact printing device. The device is made from inexpensive materials, and it is easily assembled by hand; this method is thus accessible to a wide range of laboratories and budgets. A single device was used to print over 2500 spots in less than three minutes at a density of 16 spots per square centimetre. This method provides a new tool to pattern biochemicals-reagents, antigens, proteins, and DNA-on planar substrates. The accuracy of the volume of fluid delivered in simple paper-to-paper printing is low, and although the pattern transfer is rapid, it is better suited for qualitative than accurate, quantitative work. By patterning the paper to which the transfer occurs using wax printing or an equivalent technique, accuracy increases substantially.     

Novel deletion of the E3A ubiquitin protein ligase gene detected by multiplex ligation-dependent probe amplification in a patient with Angelman syndrome

Angelman syndrome (AS) is a severe neurobehavioural disorder caused by failure of expression of the maternal copy of the imprinted domain located on 15q11-q13. There are different mechanisms leading to AS: maternal microdeletion, uniparental disomy, defects in a putative imprinting centre, mutations of the E3 ubiquitin protein ligase (UBE3A) gene. However, some of suspected cases of AS are still scored negative to all the latter mutations. Recently, it has been shown that a proportion of negative cases bear large deletions overlapping one or more exons of the UBE3A gene. These deletions are difficult to detect by conventional gene-scanning methods due to the masking effect by the non-deleted allele. In this study, we have used for the first time multiplex ligation-dependent probe amplification (MLPA) and comparative multiplex dosage analysis (CMDA) to search for large deletions affecting the UBE3A gene. Using this approach, we identified a novel causative deletion involving exon 8 in an affected sibling. Based on our results, we propose the use of MLPA as a fast, accurate and inexpensive test to detect large deletions in the UBE3A gene in a small but significant percentage of AS patients.     

KAM for quasi-linear and fully nonlinear forced perturbations of Airy equation

We prove the existence of small amplitude quasi-periodic solutions for quasi-linear and fully nonlinear forced perturbations of the linear Airy equation. For Hamiltonian or reversible nonlinearities we also prove their linear stability. The key analysis concerns the reducibility of the linearized operator at an approximate solution, which provides a sharp asymptotic expansion of its eigenvalues. For quasi-linear perturbations this cannot be directly obtained by a KAM iteration. Hence we first perform a regularization procedure, which conjugates the linearized operator to an operator with constant coefficients plus a bounded remainder. These transformations are obtained by changes of variables induced by diffeomorphisms of the torus and pseudo-differential operators. At this point we implement a Nash–Moser iteration (with second order Melnikov non-resonance conditions) which completes the reduction to constant coefficients.     

On families of quadratic surfaces having fixed intersections with two hyperplanes

We investigate families of quadrics all of which have the same intersection with two given hyperplanes. The cases when the two hyperplanes are parallel and when they are nonparallel are discussed. We show that these families can be described with only one parameter and describe how the quadrics are transformed as the parameter changes. This research was motivated by an application in mixed integer conic optimization. In that application, we aimed to characterize the convex hull of the union of the intersections of an ellipsoid with two half-spaces arising from the imposition of a linear disjunction.     

Dithioether ligands containing a 2,6‐disubstituted pyridine linker with two thioether‐heterocycle arms

The structure of 2,6‐bis(2‐pyridyltsulfanylmethyl)pyridine (pytmp), (I), C₁₇H₁₅N₃S₂, presents a twisted conformation, with the three planar moieties almost perpendicular to each other. The structures of two related derivatives, namely 2,6‐bis(6‐methyl‐2‐pyridylsulfanylmethyl)pyridine (mpytmp), (II), C₁₉H₁₉N₃S₂, and 2,6‐bis(4‐methyl‐2‐pyrimidylsulfanylmethyl)pyridine (mprtmp) n‐pentane hemisolvate, (III), C₁₇H₁₇N₅S₂·0.5C₅H₁₂, present extended planar fragments with just one quasi‐perpendicular arylsulfanylmethyl side arm, such that the molecules are folded in an L‐shaped conformation. All three conformations appear different from those adopted by similar compounds, demonstrating the great flexibility of such species, although such differences in conformational behaviour might drive specific coordination modes.     

Phosphido‐diphosphine pincer group 3 complexes as efficient initiators for lactide polymerization

New Group 3 metal complexes of the type [LM(CH₂SiMe₃)₂(THF)_n] supported by tridentate phosphido‐diphosphine ligands [(o‐C₆H₄PR₂) ₂ PH; L1‐H : R = iPr; L2‐H : R = Ph] have been synthesized by reaction of L1‐H and L2‐H with [M(CH₂SiMe₃)₃(THF)₂)] (M = Y and Sc). All the new complexes [(o‐C₆H₄PR₂) ₂ PM(CH₂SiMe₃)₂(THF)_n] [M = Y, R = iPr (1), R = Ph (2); M = Sc, R = iPr (3), R = Ph (4)] were studied as initiators for the ring opening polymerization of lactide. The yttrium complexes ( 1 and 2 ) exhibited high activity and good polymerization control, shown by the linear fits in the plot of number‐averaged molecular weight (M_n) versus the percentage conversion and versus the monomer/initiator ratio and by the low polydispersity index values. Interestingly, very good molar‐mass control was observed even when L ‐Lactide was polymerized in the absence of solvent at 130 °C. A good molar‐mass control but lower activities were observed in the polymerization reaction of lactide promoted by the analogous scandium complexes 3 and 4 . © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1374–1382, 2010