Hydrophobic cryogels for DNA adsorption: Effect of embedding of monosize microbeads into cryogel network on their adsorptive performances

As alternative hydrophobic adsorbent for DNA adsorption, supermacroporous cryogel disks were synthesized via free radical polymerization. In this study, we have prepared two kinds of cryogel disks: (i) poly(2‐hydroxyethyl methacrylate‐N‐methacryloyl‐l ‐tryptophan) [p(HEMA‐MATrp)] cryogel containing specific hydrophobic ligand MATrp; and (ii) monosize p(HEMA‐MATrp) particles synthesized via suspension polymerization embedded into p(HEMA) cryogel structure to obtain p(HEMA‐MATrp)/p(HEMA) composite cryogel disks. These cryogel disks containing hydrophobic functional group were characterized via swelling studies, Fourier transform infrared spectroscopy, elemental analysis, surface area measurements and scanning electron microscopy. DNA adsorption onto both p(HEMA‐MATrp) cryogel and p(HEMA‐MATrp)/p(HEMA) composite cryogels was investigated. Maximum adsorption of DNA on p(HEMA‐MATrp) cryogel was found to be 15 mg/g polymer. Otherwise, p(HEMA‐MATrp)/p(HEMA) composite cryogels significantly increased the DNA adsorption capacity to 38 mg/g polymer. Composite cryogels could be used repeatedly without significant loss on adsorption capacity after 10 repetitive adsorption–desorption cycles. Copyright © 2013 John Wiley & Sons, Ltd.     

Molecularly Imprinted Supermacroporous Cryogels for Myoglobin Recognition

Myoglobin is a primary iron, and oxygen-binding protein of muscle tissues and levels can be an important diagnostic biomarker for acute myocardial infarction, myocardial necrosis, or other cardiac diseases. The establishment of myoglobin recognition systems is important because of its protein’s structural and functional values in physiology, biochemistry, and diagnostic value in some damaged muscle tissue and cardiac diseases. For this purpose, we used molecular imprinting technique for myoglobin recognition from aqueous solutions and human plasma. In the first step, myoglobin-imprinted poly(hydroxyethyl methacrylate) (PHEMA) cryogels (MGb-MIP) were prepared, and optimum myoglobin adsorption conditions were determined. Selectivity experiments have been done with the competitive proteins, and myoglobin adsorption from IgG and albumin-free human plasma was studied. The purity of the desorbed samples was determined with SDS-PAGE. The desorption efficiency and reusability of the MGb-MIP cryogels were tested, and it was shown that without any significant loss in the adsorption capacity, MGb-MIP cryogels can be used a number of times for myoglobin recognition and separation.     

Residual stress/strain analysis in thin films by X-ray diffraction

Residual stresses are found in the majority of multilayer thin film structures used in modem technology. The measurement and modeling of such stress fields and the elucidation of their effects on structural reliability and device operation have been a “growth area” in the literature, with contributions from authors in various scientific and engineering disciplines.

In this article the measurement of the residual stresses in thin film structures with X-ray diffraction techniques is reviewed and the interpretation of such data and their relationship to mechanical reliability concerns are discussed.     

Iridium-catalyzed hydrogenation of N-heterocyclic compounds under mild conditions by an outer-sphere pathway

A new homogeneous iridium catalyst gives hydrogenation of quinolines under unprecedentedly mild conditions-as low as 1 atm of H(2) and 25 °C. We report air- and moisture-stable iridium(I) NHC catalyst precursors that are active for reduction of a wide variety of quinolines having functionalities at the 2-, 6-, and 8- positions. A combined experimental and theoretical study has elucidated the mechanism of this reaction. DFT studies on a model Ir complex show that a conventional inner-sphere mechanism is disfavored relative to an unusual stepwise outer-sphere mechanism involving sequential proton and hydride transfer. All intermediates in this proposed mechanism have been isolated or spectroscopically characterized, including two new iridium(III) hydrides and a notable cationic iridium(III) dihydrogen dihydride complex. DFT calculations on full systems establish the coordination geometry of these iridium hydrides, while stoichiometric and catalytic experiments with the isolated complexes provide evidence for the mechanistic proposal. The proposed mechanism explains why the catalytic reaction is slower for unhindered substrates and why small changes in the ligand set drastically alter catalyst activity.     

Conversion of methanol to 2,2,3-trimethylbutane (triptane) over indium(III) iodide

InI3 is able to catalyze the conversion of methanol to a mixture of hydrocarbons at 200 degrees C with one highly branched alkane, 2,2,3-trimethylbutane (triptane), being obtained in high selectivity. The mechanism for InI3-catalyzed reactions appears to be basically the same as that proposed for the previously studied ZnI2-catalyzed system in which sequential methylation of olefins is followed by competing reactions of the resulting carbocation: proton loss to give the next olefin vs hydride transfer to give the corresponding alkane. Although the reaction conditions and typical triptane yields achievable with ZnI2 and InI3 are quite similar, the two systems behave rather differently in a number of important particulars, including significant differences between the detailed product distributions. Most of the differences in behavior can be ascribed to the stronger Lewis acidity of InI3, including the ability to activate some alkanes, the higher activity for methylation of arenes, and the fact that methanol conversion can be observed at somewhat lower temperatures with InI3 than with ZnI2.     

Strong oscillations in molecular valence photoemission intensities

Photoemission from the two outermost ionizations [highest occupied molecular orbitals (HOMO and HOMO-1)] of Mg(eta(5)-C(5)H(5))(2) has been studied with synchrotron radiation in the gas phase. Strong oscillations in the HOMO-1/HOMO ratio, qualitatively similar to those well-known for fullerenes, are found. Excellent agreement with the experimental ratio is provided by accurate cross section calculations both at the density-functional theory and time-dependent density-functional theory level, indicating that a many electron response has a minor role for this effect. A comparison with the calculated values for other metal sandwich compounds indicate that the presence of oscillations is a widespread phenomenon, and a potential source of interesting information on the structural and electronic properties of the target molecule.     

Modeling sequence scrambling and related phenomena in mixed-model production lines

In this paper we examine the various effects that workstations and rework loops with identical parallel processors and stochastic processing times have on the performance of a mixed-model production line. Of particular interest are issues related to sequence scrambling. In many production systems (especially those operating on just-in-time or in-line vehicle sequencing principles), the sequence of orders is selected carefully to optimize line efficiency while taking into account various line balancing and product spacing constraints. However, this sequence is often altered due to stochastic factors during production. This leads to significant economic consequences, due to either the degraded performance of the production line, or the added cost of restoring the sequence (via the use of systems such as mix banks or automated storage and retrieval systems). We develop analytical formulas to quantify both the extent of sequence scrambling caused by a station of the production line, and the effects of this scrambling on downstream performance. We also develop a detailed Markov chain model to analyze related issues regarding line stoppages and throughput. We demonstrate the usefulness of our methods on a range of illustrative numerical examples, and discuss the implications from a managerial point of view.     

Thiocyanate linkage isomerism in a ruthenium polypyridyl complex

Ruthenium polypyridyl complexes have seen extensive use in solar energy applications. One of the most efficient dye-sensitized solar cells produced to date employs the dye-sensitizer N719, a ruthenium polypyridyl thiocyanate complex. Thiocyanate complexes are typically present as an inseparable mixture of N-bound and S-bound linkage isomers. Here we report the synthesis of a new complex, [Ru(terpy)(tbbpy)SCN][SbF(6)] (terpy = 2,2';6',2'-terpyridine, tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine), as a mixture of N-bound and S-bound thiocyanate linkage isomers that can be separated based on their relative solubility in ethanol. Both isomers have been characterized spectroscopically and by X-ray crystallography. At elevated temperatures the isomers equilibrate, the product being significantly enriched in the more thermodynamically stable N-bound form. Density functional theory analysis supports our experimental observation that the N-bound isomer is thermodynamically preferred, and provides insight into the isomerization mechanism.     

A model developed for acid dissolution thermodynamics of a Turkish bentonite

A model was proposed to calculate some thermodynamic parameters for the acid dissolution process of a bentonite containing a calcium-rich smectite as clay mineral along with quartz, opal and feldspar as impurities. The bentonite sample was treated with H₂SO₄ by applying dry method in the temperature range 50–150°C for 24 h. The acid content in the dry bentonite-sulphuric acid mixture was 45 mass%. The total content (x) of Al₂O₃, Fe₂O₃ and MgO remained in the undissolved sample after treatment was taken as an equilibrium parameter. An apparent equilibrium constant, K _a, was calculated for each temperature by assuming K _a=(x _m−x)/x where x _m is the total oxide content of the natural bentonite. Also, an apparent change in Gibbs free energy, ΔG _a^o, was calculated for each temperature by using the K _a value. The graphs of lnK _a vs. 1/T and ΔG _a^o vs. T were drawn and then the real change in both the enthalpy, ΔH ^o and the entropy, ΔS ^o, values were calculated from the slopes of the straight lines, respectively. Inversely, real ΔG ^o and K values were calculated from the real ΔH ^o and ΔS ^o values through ΔG ^o = −RT ln K = ΔH ^o − TΔS ^o equation. The best ΔH ^o and ΔS ^o fittings to this relation were found to be 65687 J mol⁻¹ and 164 J mol⁻¹K⁻¹, respectively.     

Effects of boundary conditions and anisotropy on elastically bent silicon

In four-point bending, the rollers that are used for load application impose additional constraints on the specimen that affect the anticlastic specimen curvature and cause the specimen displacement and stress profiles to deviate from the pure beam bending case. In this study, x-ray microdiffraction is used to map both the principal and anticlastic curvatures of elastically bent, rectangular (100)-type Si strips possessing width:thickness ratios of 40:1. We quantify the amount of roller constraint and show that the region over which the anticlastic specimen curvature is affected away from the roller is approximately five times the roller diameter. Consequently, for bending tests used to determine Poisson's ratio, if a region on the sample that is free from roller effects is not chosen, measurement errors as high as 46% can occur. Furthermore, we show that, due to the anisotropy of single crystal Si, this roller-constraining effect depends on crystallographic orientation and is more pronounced when the principal bending axis lies along the <100> direction as compared with the <100> direction.