Determination of unreacted 2,4-toluene diisocyanate (2,4TDI) and 2,6-toluene diisocyanate (2,6TDI) in foams at ultratrace level by using HPLC-CIS-MS-MS

Isocyanates can cause occupational asthma. By using available HPLC-UVF methods, isocyanates can be quantified only at levels above 1% of the Permissible Exposure Limits (PEL). Once sensitized, workers can react to concentrations below these limits of detection (LOD) making these methods insufficiently sensitive to adequately evaluate trace amounts of isocyanates present in air or in materials at safe levels for sensitized workers. This article describes a novel method for isocyanate analysis allowing the quantification of 2,4TDI and 2,6TDI monomers at very low concentrations using HPLC-CIS-MS-MS. The method's sensitivity increases with a decrease in the alkali radius. The LOD is 0.039 ng mL(-1) for 2,4TDI and 0.100 ng mL(-1) for 2,6TDI in solution when lithium is the alkali adduct, which is 20 times more sensitive than HPLC-UVF method. This new method allows determination in foam at levels of 0.078 ng g(-1) for 2,4TDI and 0.200 ng g(-1) for 2,6TDI respectively, for a 0.5 g foam sample. This is more than 100 times more sensitive than other methods for determining free monomers in solid materials. Analytical reproducibility and precision are better than 92% and 93% for both diisocyanate monomers. The use of HPLC-UVF conventional method failed to detect unreacted isocyanates in foam samples, but TDI monomers were quantified by HPLC-CIS-MS-MS.     

A study of fused silica micro/nano patterning by focused-ion-beam

A dual-beam scanning electron microscopy (SEM)/focused-ion-beam (FIB) system was used to pattern fused silica substrates coated with a 15 nm thin Cr layer. The dimensions of fabricated features together with their surface morphology and profiles were investigated by SEM and atomic force microscopy (AFM). The study demonstrated that with the increase of the ion beam fluence the sputtering rate of the fused silica decreased non-linearly. Also, it was found that initially the sputtering rate increased with the increase of the beam current, after reaching a maximum value, it started decreasing when further beam current increment was performed. Compared with unprocessed areas, the surface finish of the features fabricated by FIB exhibited a significant improvement, and the ion fluence influence on the surface roughness of trenches with low aspect ratios could be considered as negligible. Using a fine beam probe, nano-gratings in the form of grooves with a width down to 54 nm and an aspect ratio higher than three were fabricated. The study showed that FIB machining could be an alternative technology to e-beam lithography for producing fused silica templates for UV nanoimprinting.     

Linear combinations of heuristics for examination timetabling

Although they are simple techniques from the early days of timetabling research, graph colouring heuristics are still attracting significant research interest in the timetabling research community. These heuristics involve simple ordering strategies to first select and colour those vertices that are most likely to cause trouble if deferred until later. Most of this work used a single heuristic to measure the difficulty of a vertex. Relatively less attention has been paid to select an appropriate colour for the selected vertex. Some recent work has demonstrated the superiority of combining a number of different heuristics for vertex and colour selection. In this paper, we explore this direction and introduce a new strategy of using linear combinations of heuristics for weighted graphs which model the timetabling problems under consideration. The weights of the heuristic combinations define specific roles that each simple heuristic contributes to the process of ordering vertices. We include specific explanations for the design of our strategy and present the experimental results on a set of benchmark real world examination timetabling problem instances. New best results for several instances have been obtained using this method when compared with other constructive methods applied to this benchmark dataset.     

Invited Lecture. Smectic A polymorphism from low to high molar mass systems

The polymorphism of smectic A phases in low molecular weight (L.M.W.) liquid crystals is associated with strong anomalies in the period defining the layers. The smectic A phases of liquid-crystalline comb-like polymers also have various modes of spacing. However, the behaviour of these polymer phases shows some peculiarities compared with L.M.W. compounds, especially due to the main chain which takes part in the smectic arrangement. To specify further the S_A polymorphism in high molar mass systems, the use of side chain polymers with partial fixation appears to be very promising: either taking advantage of better compatibility and lower viscosity in order to describe binary diagrams with L.M.W. mesogens, or through the partial insertions of long polar side groups known to generate anomalies of periodicity as for L.M.W. compounds.     

Brauer characters with cyclotomic field of values

It has been shown in an earlier paper [G. Navarro, Pham Huu Tiep, Rational Brauer characters, Math. Ann. 335 (2006) 675-686] that, for any odd prime p, every finite group of even order has a non-trivial rational-valued irreducible p-Brauer character. For p=2 this statement is no longer true. In this paper we determine the possible non-abelian composition factors of finite groups without non-trivial rational-valued irreducible 2-Brauer characters. We also prove that, if p≠q are primes, then any finite group of order divisible by q has a non-trivial irreducible p-Brauer character with values in the cyclotomic field Q(exp(2πi/q)).     

Microdeformation behavior in nanotemplated epoxy thermosets: A study with in situ tensile deformation technique in transmission electron microscopy

Microdeformation behavior in nanostructured block copolymer‐toughened epoxy resins, or templated epoxy thermosets, was studied using an in situ tensile deformation technique performed directly in a transmission electron microscope. The observed microdeformation modes were found to correlate well with the macroscopic mechanical properties of the materials. In the order of decreasing macroscopic fracture toughness, the microdeformation modes were observed to change from large uniform plastic deformation over an extensive area, to localized plastic deformation bands, to little plastic deformation observed in the most brittle material. A similar trend was also observed when samples of the same material were tested at different temperatures, reflecting changes in the deformation mechanism as a function of temperature. Structural defects were observed in nanotoughening phases when plastic deformation was observed. The implication of the observed microdeformation modes to the macroscopic toughening mechanisms is discussed in the context of the micromorphology of the nanometer sized toughening phases and parameters of the epoxy matrix chemistry such as bromination, molecular weight, and interfacial miscibility. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 393–406, 2009     

Synthesis,photopolymerization, and adhesive properties of new bisphosphonic acid monomers for dental application

Four new monomers, 3‐(N‐methylacrylamido)propylidenebisphosphonic acid, 3‐(N‐propyl‐acrylamido)propylidenebisphosphonic acid, 3‐(N‐hexylacrylamido)propylidenebisphosphonic acid, and 3‐(N‐octylacrylamido)propylidenebisphosphonic acid, have been synthesized in good yields and fully characterized by ¹H, ¹³C, ³¹P NMR, and HRMS. The copolymerization of these monomers with N,N′‐diethyl‐1,3‐bis(acrylamido)propane (DEBAAP) has been investigated with differential scanning calorimetry. These mixtures show a higher reactivity than DEBAAP. New self‐etch dental primers, based on these acrylamide monomers, have been formulated. Dentin shear bond strength measurements have shown that primers based on these bisphosphonic acids assure a strong bond between the tooth substance and a dental composite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5258–5271, 2009     

Straightforward access to new vinca-alkaloids via selective reduction of a nitrile containing anhydrovinblastine derivative

A procedure to exclusively obtain 3′S-cyanoanhydrovinblastine 12 from two naturally occurring vinca-alkaloids (catharanthine and vindoline) in one step with good yield is described. Stereoselective reductions of 12, providing straightforward access to three new vinca-alkaloids, including two diastereomers 3′S-cyano-(4′R,5′-dihydro)-anhydrovinblastine and 3′S-cyano-(4′S,5′-dihydro)-anhydrovinblastine as well as (3′S-aminomethyl)-(4′S,5′-dihydro)-anhydrovinblastine in good yields is also reported.