Creeping flow analysis of an integrated microfluidic device for rheometry

This paper analyzes flow of a power-law fluid in a microfluidic device for the purpose of discovering an algorithm for rheometry. Previous investigations have shown that measurement of the velocity field or the pressure field and the inlet flow rate in a microfluidic T-junction allow determination of rheological parameters uniquely. However, the range of shear induced within the flow domain was limited by the constant pressure drop applied across the micro-device. To avoid this control restriction and further develop our inverse technique, a constant flow rate system was investigated. With this configuration, the flow rate can be set appropriately to achieve a desired shear range and the rheological parameters can be inferred from the measurement of mean pressure at the inlet and at the junction. By assuming creeping flow conditions and the existence of a Hagen-Poiseuille-like law for the relationship between the pressure drop and the volumetric flow rate, the analysis produces an algorithm that is self-consistent (demonstrates the Hagen-Poiseuille law) and permits the inference of the power-law parameters from the ratio of any two field variables measured over a region (averaged), the pressure drop, and the volumetric flow rate.     

Further results on the maximum size of a hole in an incomplete t‐wise balanced design with specified minimum block size*

Kreher and Rees 3 proved that if h is the size of a hole in an incomplete balanced design of order υ and index λ having minimum block size , then, They showed that when t = 2 or 3, this bound is sharp infinitely often in that for each h ≥ t and each k ≥ t + 1, (t,h,k) ≠(3,3,4), there exists an ItBD meeting the bound. In this article, we show that this bound is sharp infinitely often for every t, viz., for each t ≥ 4 there exists a constant C_t > 0 such that whenever (h ? t)(k ? t ? 1) ≥ C_t there exists an ItBD meeting the bound for some λ = λ(t,h,k). We then describe an algorithm by which it appears that one can obtain a reasonable upper bound on C_t for any given value of t. © 2002 Wiley Periodicals, Inc. J Combin Designs 10: 256–281, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10014     

Thermogravimetric studies of the decomposition of red lead (Pb3O4)

TG measurements have been performed on red lead under (a) isothermal (b) dynamic conditions, under a constant flow of nitrogen.The results have been analyzed to establish the decomposition kinetics and calculate the activation energies.In the case of isothermal decomposition, it is concluded that rate of diffusion of gaseous products is the controlling factor, while in dynamic decomposition nucleation and growth within the Pb₃O₄ particles is important.

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Zusammenfassung TG-Messungen wurden an Zinoberrot unter a) isothermen und b) dynamischen Bedingungen, in einem konstanten Stickstoffstrom durchgeführt. Die Ergebnisse wurden analysiert um die Zersetzungskinetik zu ermitteln und die Aktivierungsenergien zu berechnen. Im Falle der isothermen Zersetzung wurde gefolgert, da\ die Diffusionsgeschwindigkeit der gasförmigen Produkte der steuernde Faktor ist, wÄhrend bei der dynamischen Zersetzung die Keimbildung und das Wachstum innerhalb der Pb₃O₄-Teilchen von Bedeutung ist.

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Résumé On a effectué des mesures TG sur du cinabre en conditions a) isothermes et b) dynamiques, sous courant constant d'azote. On a analysé les résultats afin d'établir la cinétique de la décomposition et de calculer les énergies d'activation. Dans le cas de la décomposition isotherme, on a conclu que la vitesse de la diffusion des produits gazeux était le facteur contrÔlant la réaction, tandis que lors de la décomposition dynamique la nucléation et la croissance des particules de Pb₃O₄ jouaient un rÔle important.

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. . , . Pb₃O₄.

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The authors thank Nobel's Explosives Co. Ltd. for financial support and supply of materials, and Science Research Council for granting a Co-operating Award in Science and Engineering (CASE) research studentship to one of us (S. S. Al-Kazraji).     

Speciation of strontium in human and bovine milk

The speciation of strontium in human and bovine milk has been computed using a chemical equilibrium model and the ECCLES program. The calculations show     

Are J(Si-H) NMR coupling constants really a probe for the existence of nonclassical H-Si interactions?

A series of hydridosilyl complexes of tantalum, Cp(ArN)Ta(PMe3)(H)(SiClnR3-n) (n = 0-3), was prepared and studied by 29Si NMR, X-ray diffraction, and DFT calculations. An unprecedented increase of the J(Si-H) coupling constant between the hydride and silyl ligands from 14 Hz for n = 0 to 50 Hz n = 3 was observed, which however, according to DFT calculations, does not correspond to stronger bonding interaction between silicon and hydride ligands, with the strongest interaction being for n = 1.     

Hypochlorite-mediated fragmentation of hyaluronan, chondroitin sulfates, and related N-acetyl glycosamines: evidence for chloramide intermediates, free radical transfer reactions, and site-specific fragmentation

Myeloperoxidase released from activated phagocytes reacts with H(2)O(2) in the presence of chloride ions to give hypochlorous acid. This oxidant has been implicated in the fragmentation of glycosaminoglycans, such as hyaluronan and chondroitin sulfates. In this study it is shown that reaction of HOCl with glycosaminoglycans and model compounds yields chloramides derived from the N-acetyl function of the glycosamine rings. The results of EPR spin trapping and product studies are consistent with the formation of amidyl radicals from these chloramides via both metal ion-dependent and -independent processes. In the case of glycosaminoglycan-derived amidyl radicals, evidence has been obtained in studies with model glycosides that these radicals undergo rapid intramolecular abstraction reactions to give carbon-centered radicals at C-2 on the N-acetyl glycosamine rings (via a 1,2-hydrogen atom shift) and at C-4 on the neighboring uronic acid residues (via 1,5-hydrogen atom shifts). The C-4 carbon-centered radicals, and analogous species derived from model glycosides, undergo pH-independent beta-scission reactions that result in glycosidic bond cleavage. With N-acetyl glucosamine C-1 alkyl glycosides, product formation via this mechanism is near quantitative with respect to chloramide loss. Analogous reactions with the glycosaminoglycans result in selective fragmentation at disaccharide intervals, as evidenced by the formation of "ladders" on gels; this selectivity is less marked under atmospheric oxygen concentrations than under anoxic conditions, due to competing peroxyl radical reactions. As the extracellular matrix plays a key role in mediating cell adhesion, growth, activation, and signaling, such HOCl-mediated glycosaminoglycan fragmentation may play a key role in disease progression and resolution, with the resulting fragments modulating the magnitude and quality of the immune response in inflammatory conditions.     

Unprecedented conversion of triethylamine and disulfur dichloride into a thienopentathiepin and a heptathiocane

[reaction: see text] In a remarkable cascade reaction, triethylamine is converted into the thienopentathiepin 2a and the heptathiocane 3a by a preequilibrated solution of disulfur dichloride and DABCO in chloroform.     

Synthesis of thiadiazole, dithietane, and imine derivatives of the [1,2]dithiolo[1,4]thiazine ring system

We report the synthesis of some new polysulfur-nitrogen heterocyclics by cycloaddition reactions to the thioketo group of readily available tricyclic 1,2-dithiole-3-thiones. Thus treatment of bis[1,2]dithiolo[1,4]thiazine ketothione 1 with diaryl nitrile imines generated from hydrazonoyl chlorides 2a-g gave [1,3,4]thiadiazolylidenyl[1,2]dithiolo[1,4]thiazines 4a-g in high yield. Compounds 4a-f, bearing the same substituents in both aryl groups, were stable but the analogous 4g,h with a p-nitrophenyl group on carbon gave the bis[1,2]dithiolo[1,4]thiazine dione 9, probably by cycloreversion and hydrolysis during chromatography. Treatment of 1, the bis[1,2]dithiolopyrrole ketothione 13, and dithione 12 with ethoxycarbonyl azide 11 gave imines 12 and 15 and bisimine 16, respectively, by an alternative fragmentation of the initial cycloadduct in which the 1,2-dithiole ring is retained. Reaction of 1 with TosMIC gave the imino-1,3-dithietane 17.     

Submicrometer fiber-optic Fabry-Perot interferometer formed by use of the Langmuir-Blodgett technique

The fabrication of an optical cavity at the distal end of an optical fiber has been achieved by Langmuir-Blodgett (LB) deposition of tricosanoic acid. This technique allows nanometer-scale control over the cavity length to a total thickness of ~0.5 microm . The cavity has been shown to act interferometrically and, thus, has potential sensing applications.