Programmable Polymer‐Based Supramolecular Temperature Sensor with a Memory Function

A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT⁴⁺ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.     

Understanding and improving direct UV detection of monosaccharides and disaccharides in free solution capillary electrophoresis

Direct UV detection of carbohydrates in free solution capillary electrophoresis at 270 nm is made possible by a photo-oxidation reaction. Glucose, rhamnose and xylose were shown to have unique UV absorption spectra hypothesizing different UV absorbing intermediates for their respective photo-oxidation. NMR spectroscopy of the photo-oxidation end products proved they consisted of carboxylates and not malondialdehyde as previously theorized and that oxygen thus plays a key role in the photo-oxidation pathway. Adding the photo-initiator Irgacure^® 2959 in the background electrolyte increased sensitivity by 40% at an optimum concentration of 1 × 10⁻⁴ mM and 1 × 10⁻⁸ mM for conventional 50 μm i.d. capillaries and for the corresponding extended light path capillaries, respectively.     

The synthesis of a pyrrole-functionalized cyclobis(paraquat-p-phenylene) derivative and its corresponding [2]rotaxane and [2]catenane and their subsequent deposition onto an electrode surface

We report the convenient synthesis of a pyrrole-functionalized tetracationic cyclophane, [2]rotaxane, and [2]catenane. X-ray crystallography has confirmed the interlocked structure of the catenane. We have investigated the solution properties of these systems using solution electrochemistry, NMR, and UV-vis spectroscopy. We have also demonstrated that it is possible to immobilize these systems onto a platinum working electrode surface. We have shown that films of the cyclophane have the ability to undergo complexation with a dialkyloxynaphthalene derivative.     

Synthesis of methacrylate derivatives oligomers by dithiobenzoate‐RAFT‐mediated polymerization

Reversible addition fragmentation chain transfer (RAFT) was used to synthesize methacrylic acid oligomers and oligo(methacrylic acid)‐b‐poly(methyl methacrylate) (PMAA‐b‐PMMA) with targeted degree of polymerization ≈ 10. Characterization is by size‐exclusion chromatography (SEC) and electrospray mass‐spectrometry. SEC data are presented as hydrodynamic volume distributions (HVDs), the only proper means to present comparative and meaningful SEC data when there is no unique relationship between size and molecular weight. The RAFT agent, (4‐cyanopentanoic acid)‐4‐dithiobenzoate (CPADB), produced dithiobenzoic acid as a side product during the polymerization of methacrylate derivatives. Precipitation in diethyl ether proved to be an easy way to remove this impurity from the PMAA‐RAFT oligomers. Both unpurified and purified macro‐RAFT agent were used to prepare amphiphilic PMAA‐b‐PMMA copolymers. Diblock copolymer prepared from the purified PMAA homopolymer had a narrower HVD in comparison to those obtained from the equivalent unpurified macro‐RAFT agent. This work shows that while cyanoisopropyl‐dithiobenzoate or CPADB are good RAFT agents for methacrylate derivatives, they exhibit some instability under typical polymerization conditions, and thus when oligomers are targeted, optimal control requires checking for the degradation product and appropriate purification steps when necessary (the same effect is present for larger polymers but is unimportant). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2277–2289, 2008     

On the Synthesis of Pyrrolobenzo[<Emphasis Type="Italic">b</Emphasis>]thieno[1,4]diazepines

Summary. 2-Amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile was converted into the corresponding 2-(pyrrol-1-yl) derivative, followed by reduction of the latter compound into the corresponding amine. This amine and its acyl, aroyl, and arylidene derivatives were used as synthons in the synthesis of several title compounds.     

Global convergence of descent processes for solving non strictly monotone variational inequalities

This paper addresses the question of global convergence of descent processes for solving monotone variational inequalities defined on compact subsets ofR ⁿ . The approach applies to a large class of methods that includes Newton, Jacobi and linearized Jacobi methods as special cases. Furthermore, strict monotonicity of the cost mapping is not required.Research supported by NSERC grant A5789.     

Investigation on laser brazing AA6056 Al alloy to XC18 low-carbon steel

Based on the studies of influence of YAG laser heating conditions for Al alloy melt and steel on wettability,the mechanics of the laser overlap braze welding of 6056 Al and XC18 steel sheet has been investigated.Under the temperature range which is above the melting point of the Al alloy and below the melting point of the steel, two dissimilar metals can be joined by means of laser braze welding. There is no crack observed in the joining area, i.e. Al-Fe intermetallic phase (Fe3Al/FeAl/FeAl3/Fe2Al5) layer formed by solution and diffusion between liquid-solid interface. The temperature range can be defined as the process temperatures of laser braze welding of Al-Fe materials. Selecting a higher laser heating temperature can improve the wettability of Al melt to steel surface, but the intermetallic phase layer is also thicker. When the laser heating temperature is so high that the joining surface of steel is melted, there is a crack trend in the joining area.     

Adaptive mesh refinement for the control of cost and quality in finite element analysis

Adaptive strategies are a necessary tool to make finite element analysis applicable to engineering practice. In this paper, attention is restricted to mesh adaptivity. Traditionally, the most common mesh adaptive strategies for linear problems are used to reach a prescribed accuracy. This goal is best met with an h-adaptive scheme in combination with an error estimator. In an industrial context, the aim of the mechanical simulations in engineering design is not only to obtain greatest quality but more often a compromise between the desired quality and the computation cost (CPU time, storage, software, competence, human cost, computer used). In this paper, we propose the use of alternative mesh refinement criteria with an h-adaptive procedure for 3D elastic problems. The alternative mesh refinement criteria (MR) are based on: prescribed number of elements with maximum accuracy, prescribed CPU time with maximum accuracy and prescribed memory size with maximum accuracy. These adaptive strategies are based on a technique of error in constitutive relation (the process could be used with other error estimators) and an efficient adaptive technique which automatically takes into account the steep gradient areas. This work proposes a 3D method of adaptivity with the latest version of the INRIA automatic mesh generator GAMHIC3D.     

Simultaneous Determination of Nickel and Cobalt as Chelates with 1-(2-Pyridylazo)-2-naphthol Using an LC Switching Column Method

A simple liquid chromatographic method was developed for the separation and simultaneous determination of cobalt and nickel as chelates with 1-(2-pyridylazo)-2-naphthol (PAN). The method, using a switching column technique for the on-line purification and separation, enables to reach the sub-microgram per litre concentration level excluding off-line sample treatment with the exception of the derivatization reaction. Two small-sized columns packed with CN- and C₄-bonded stationary phases were selected and used considering their complementary behaviour with respect to chelated Co and Ni ions. The analysis was performed within 10 min using an optimised eluent (water–acetonitrile–methanol–tetrahydrofuran, 40:45:10:5, v/v/v/v) containing Tween 40 (10^?3 M) and acetate buffer (5 × 10^?3 M, pH 4.8). Detection was performed by UV-vis spectrophotometry (λ = 565 nm) permitting to reach quantification limits of 0.9 and 0.5 μg L^?1 for Co and Ni, respectively.