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.     

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.     

A Hermite collocation method for the approximate solutions of high‐order linear Fredholm integro‐differential equations

In this study, a Hermite matrix method is presented to solve high‐order linear Fredholm integro‐differential equations with variable coefficients under the mixed conditions in terms of the Hermite polynomials. The proposed method converts the equation and its conditions to matrix equations, which correspond to a system of linear algebraic equations with unknown Hermite coefficients, by means of collocation points on a finite interval. Then, by solving the matrix equation, the Hermite coefficients and the polynomial approach are obtained. Also, examples that illustrate the pertinent features of the method are presented; the accuracy of the solutions and the error analysis are performed. © 2010 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 27: 1707–1721, 2011     

Scale-up and Sustainability Evaluation of Biopolymer Production from Citrus Waste Offering Carbon Capture and Utilisation Pathway

Poly(limonene carbonate) (PLC) has been highlighted as an attractive substitute to petroleum derived plastics, due to its utilisation of CO₂ and bio-based limonene as feedstocks, offering an effective carbon capture and utilisation pathway. Our study investigates the techno-economic viability and environmental sustainability of a novel process to produce PLC from citrus waste derived limonene, coupled with an anaerobic digestion process to enable energy cogeneration and waste recovery maximisation. Computational process design was integrated with a life cycle assessment to identify the sustainability improvement opportunities. PLC production was found to be economically viable, assuming sufficient citrus waste is supplied to the process, and environmentally preferable to polystyrene (PS) in various impact categories including climate change. However, it exhibited greater environmental burdens than PS across other impact categories, although the environmental performance could be improved with a waste recovery system, at the cost of a process design shift towards energy generation. Finally, our study quantified the potential contribution of PLC to mitigating the escape of atmospheric CO₂ concentration from the planetary boundary. We emphasise the importance of a holistic approach to process design and highlight the potential impacts of biopolymers, which is instrumental in solving environmental problems facing the plastic industry and building a sustainable circular economy.     

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.     

Partial Pooling in Tandem Lines with Cooperation and Blocking

For a tandem line of finite, single-server queues operating under the production blocking mechanism, we study the effects of pooling several adjacent stations and the associated servers into a single station with a single team of servers. We assume that the servers are cross-trained (so that they can work at several different stations) and that two or more servers can cooperate on the same job. For such a system, we provide sufficient conditions on the service times and sizes of the input and output buffers at the pooled station under which pooling will decrease the departure time of each job from the system (and hence increase the system throughput). We also show that pooling decreases the total number of jobs in the system at any given time and the sojourn time of each job in the system if the departure time of each job from the system is decreased by pooling and there is an arrival stream at the first station. Moreover, we provide sufficient conditions under which pooling will improve the holding cost of each job in the system incurred before any given time, and extend our results to closed tandem lines and to queueing networks with either a more general blocking mechanism or probabilistic routing. Finally, we present a numerical study aimed at quantifying the improvements in system performance obtained through pooling and at understanding which stations should be pooled to achieve the maximum benefit. Our results suggest that the improvements gained by pooling may be substantial and that the bottleneck station should be among the pooled stations in order to obtain the greatest benefit. AMS subject classification: 90B22     

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.     

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.     

Organometallic ni pincer complexes for the electrocatalytic production of hydrogen

Nonplatinum metals are needed to perform cost-effective water reduction electrocatalysis to enable technological implementation of a proposed hydrogen economy. We describe electrocatalytic proton reduction and H(2) production by two organometallic nickel complexes with tridentate pincer ligands. The kinetics of H(2) production from voltammetry is consistent with an overall third order rate law: the reaction is second order in acid and first order in catalyst. Hydrogen production with 90-95% Faradaic yields was confirmed by gas analysis, and UV-vis spectroscopy suggests that the ligand remains bound to the catalyst over the course of the reaction. A computational study provides mechanistic insights into the proposed catalytic cycle. Furthermore, two proposed intermediates in the proton reduction cycle were isolated in a representative system and show a catalytic response akin to the parent compound.     

Infinite Direct Sums of Lifting Modules

A module M over a ring R is called a lifting module if every submodule A of M contains a direct summand K of M such that A/K is a small submodule of M/K (e.g., local modules are lifting). It is known that a (finite) direct sum of lifting modules need not be lifting. We prove that R is right Noetherian and indecomposable injective right R-modules are hollow if and only if every injective right R-module is a direct sum of lifting modules. We also discuss the case when an infinite direct sum of finitely generated modules containing its radical as a small submodule is lifting.