Optical detection enhancement in porous volumetric microfluidic capture elements using refractive index matching fluids.

Porous volumetric capture elements in microfluidic sensors are advantageous compared to planar capture surfaces due to higher reaction site density and decreased diffusion lengths that can reduce detection limits and total assay time. However a mismatch in refractive indices between the capture matrix and fluid within the porous interstices results in scattering of incident, reflected, or emitted light, significantly reducing the signal for optical detection. Here we demonstrate that perfusion of an index-matching fluid within a porous matrix minimizes scattering, thus enhancing optical signal by enabling the entire capture element volume to be probed. Signal enhancement is demonstrated for both fluorescence and absorbance detection, using porous polymer monoliths in a silica capillary and packed beds of glass beads within thermoplastic microchannels, respectively. Fluorescence signal was improved by a factor of 3.5× when measuring emission from a fluorescent compound attached directly to the polymer monolith, and up to 2.6× for a rapid 10 min direct immunoassay. When combining index matching with a silver enhancement step, a detection limit of 0.1 ng mL(-1) human IgG and a 5 log dynamic range was achieved. The demonstrated technique provides a simple method for enhancing optical sensitivity for a wide range of assays, enabling the full benefits of porous detection elements in miniaturized analytical systems to be realized.

To gel or not to gel: correlating molecular gelation with solvent parameters.

Rational design of small molecular gelators is an elusive and herculean task, despite the rapidly growing body of literature devoted to such gels over the past decade. The process of self-assembly, in molecular gels, is intricate and must balance parameters influencing solubility and those contrasting forces that govern epitaxial growth into axially symmetric elongated aggregates. Although the gelator-gelator interactions are of paramount importance in understanding gelation, the solvent-gelator specific (i.e., H-bonding) and nonspecific (dipole-dipole, dipole-induced and instantaneous dipole induced forces) intermolecular interactions are equally important. Solvent properties mediate the self-assembly of molecular gelators into their self-assembled fibrillar networks. Herein, solubility parameters of solvents, ranging from partition coefficients (log P), to Henry's law constants (HLC), to solvatochromic parameters (ET(30)), and Kamlet-Taft parameters (ß, α and π), and to Hansen solubility parameters (δp, δd, δh), are correlated with the gelation ability of numerous classes of molecular gelators. Advanced solvent clustering techniques have led to the development of a priori tools that can identify the solvents that will be gelled and not gelled by molecular gelators. These tools will greatly aid in the development of novel gelators without solely relying on serendipitous discoveries. These tools illustrate that the quest for the universal gelator should be left in the hands of Don Quixote and as researchers we must focus on identifying gelators capable of gelling classes of solvents as there is likely no one gelator capable of gelling all solvents.

Spatially directed vesicle capture in the ordered pores of breath-figure polymer films.

This work describes a new method to selectively capture liposomes and other vesicle entities in the patterned pores of breath-figure polymer films. The process involves the deposition of a hydrophobe containing biopolymer in the pores of the breath figure, and the tethering of vesicles to the biopolymer through hydrophobic interactions. The process is versatile, can be scaled up and extended to the deposition of other functional materials in the pores of breath figures.

Liposomes tethered to a biopolymer film through the hydrophobic effect create a highly effective lubricating surface.

Liposomal coatings are formed on films of a biopolymer, hydrophobically modified chitosan (hm-chitosan), containing dodecyl groups as hydrophobes along the polymer backbone. The alkyl groups insert themselves into the liposome bilayer through hydrophobic interactions and thus tether liposomes, leading to a densely packed liposome layer on the film surface. Such liposomal surfaces exhibit effective lubrication properties due to their high degree of hydration, and reduce the coefficient of friction to the biologically-relevant range. The compliancy and robustness of these tethered liposomes allow retention on the film surface upon repeated applications of shear. Such liposome coated films have potential applications in biolubrication.

Soft sensor based composition estimation and controller design for an ideal reactive distillation column.

In this research work, the authors have presented the design and implementation of a recurrent neural network (RNN) based inferential state estimation scheme for an ideal reactive distillation column. Decentralized PI controllers are designed and implemented. The reactive distillation process is controlled by controlling the composition which has been estimated from the available temperature measurements using a type of RNN called Time Delayed Neural Network (TDNN). The performance of the RNN based state estimation scheme under both open loop and closed loop have been compared with a standard Extended Kalman filter (EKF) and a Feed forward Neural Network (FNN). The online training/correction has been done for both RNN and FNN schemes for every ten minutes whenever new un-trained measurements are available from a conventional composition analyzer. The performance of RNN shows better state estimation capability as compared to other state estimation schemes in terms of qualitative and quantitative performance indices.

Size-dependent diffusion in an aging colloidal glass.

Colloidal dispersions of Laponite platelets are known to age slowly from viscous sols to colloidal glasses. We follow this aging process by monitoring the diffusion of probe particles embedded in the sample via dynamic light scattering. Our results show that the time-dependent diffusion of the probe particles scales with their size at early times and for the larger particles. This implies that within this regime the measurements can be used to investigate the generalized fluctuation-dissipation theorem for this out-of-equilibrium system, where the bath temperature is replaced with an effective temperature. Simultaneous dynamic rheological measurements reveal that this effective temperature increases as a function of aging time and frequency which suggests the existence of two measured time-scale regimes. In accord with recent work by Abou [Phys. Rev. Lett. 93, 160603 (2004)], our results suggest that at probed time scales longer than the characteristic relaxation time of the Laponite dispersion the system thermalizes with the bath, whereas at shorter time scales the system is out-of-equilibrium with an effective temperature greater than the bath temperature.

Microrheology of wormlike micellar fluids from the diffusion of colloidal probes.

The microrheology of cationic micellar solutions has been investigated as a function of added organic salts using quasielastic light scattering (QELS). Two organic salts, sodium p-toluene sulfonate and sodium salicylate, were used to induce microstructural changes in cetyl trimethylammonium bromide (CTAB) micelles. The mean-squared displacement (MSD) of polystyrene probe particles embedded in CTAB micellar solutions was monitored by QELS in the single-scattering regime. Through the use of the generalized Stokes-Einstein relationship, the frequency-dependent complex shear moduli of each fluid were estimated from the Laplace transform of the corresponding MSD. The salt-induced transition from nearly spherical to elongated wormlike micelles and consequent changes in fluid response from viscous to viscoelastic are clearly captured by microrheology.

Reduced sodium-potassium dependent ATPase and its possible role in the development of hypertension in spontaneously hypertensive rats.

Ouabain-sensitive Na+-K+-ATPase activity in red cell membranes, kidney cortical tissue, myocardium and adrenal glomerulosa tissue was examined in SHR and WKY rats at 6, 9, and 12 weeks of age. Red cell membrane enzyme activity was decreased (p less than 0.001) at 9 and 12 weeks of age in SHR. This activity was negatively correlated (r = -0.69, p less than .005) with blood pressure at 9 and 12 weeks. Kidney cortical enzyme activity was also decreased (p less than 0.001) in the SHR at 9 and 12 weeks of age. This decreased kidney enzyme activity was also inversely related to 9 and 12 week blood pressures (r = -0.71, p less than 0.001), urinary Na excretion (r = -0.62, p less than .005), and urinary Ca and K excretion. Myocardial enzyme activity was not decreased until 12 weeks in the SHR, and adrenal glomerulosa activity was not different in the SHR and WKY at any of the three ages that this enzyme was measured. Of the tissues examined decreased Na+-K+-ATPase activity in the erythrocyte membrane and in kidney cortical tissue appears to coincide best with the development of hypertension in the SHR. This study lends further support to the concept that alterations in membrane cation transport may be an important factor in the development of high blood pressure in SHR.

Erythrocyte lead-binding protein after occupational exposure. II. Influence on lead inhibition of membrane Na+,K+-adenosinetriphosphatase.

Membrane Na+,K+-adenosinetriphosphatase in erythrocytes from three groups of industrially exposed Pb workers (without toxicity, with toxicity associated with high blood Pb levels, and with toxicity associated with low blood Pb levels) was inversely correlated with Pb in the membrane fraction but not significantly correlated with total erythrocyte Pb. This difference was attributable to the proportion of erythrocyte Pb bound to hemoglobin and a Pb-binding protein of molecular weight 10,000.

Immunochemical and enzymatic studies on the soluble antigens of normal human kidney.

The antigenic composition of the soluble extract from normal human kidney was determined with the combined techniques of immunological absorption, immuno-diffusion and immunoelectrophoresis. The kidney extract contained at least eleven non-serum, tissue antigens; some of them were found in the extracts of other organs, but three were kidney-specific. None of the soluble tissue antigens from human kidney was characterized as a lipoprotein; however, three of them stained with the reagent for glycoproteins. Esterase activities were also demonstrated in four non-serum, renal antigens, one of which was present only in the kidney extract and absent in the other organs extracts.