Determination of kinetic parameters for interfacial enzymatic reactions on self-assembled monolayers

This paper reports a method to characterize the kinetic constants for the action of enzymes on immobilized substrates. This example uses cutinase, a serine esterase that hydrolyzes 4-hydroxyphenyl valerate moieties that are immobilized on a self-assembled monolayer of alkanethiolates on gold. The product of the enzyme reaction is a hydroquinone, which is redox active and therefore permits the use of cyclic voltammetry to monitor the extent of reaction in situ. A kinetic model based on the Michaelis-Menten formalism is used to analyze the dependence of initial rates of reaction on both the substrate density and the enzyme concentration. The resulting value of k(cat)/K(M) for the interfacial reaction is comparable to that for a homogeneous phase reaction with a substrate of similar structure. This strategy of using monolayers presenting substrates for the enzyme and cyclic voltammetry to measure reaction rates provides quantitative and real-time information on reaction rates and permits a level of analysis of interfacial enzyme reactions that to date has been difficult to realize.     

Numerical study of surface agglomeration of ultraviolet-polymeric ink and its control during 3D nano-inkjet printing process

There is a pressing need in very small scale three-dimensional (3D) inkjet printing to control and reduce agglomeration, as agglomeration often leads to nozzle clogging. While agglomeration within ultraviolet ink has been studied, there has been, to our knowledge, no extensive studies conducted for surface agglomeration of the ink on nozzle's wall. This numerical study therefore focuses on investigating if surfactants can effectively control surface agglomeration during nanodroplet formation. Many-body dissipative particle dynamics is the numerical method of choice here. We found that small amount of surfactant of about 1 wt % is sufficient to effectively reduce ink deposition on the nozzle's wall. However, by using the properties of a commercially available surfactant, sodium dodecyl sulfate, it was found that the maximum reduction achieved by its addition is only 60%. Thus, further physical or chemical deagglomeration techniques are required, and we show that by considering these other techniques, reduction of surface agglomeration to nearly 92% can be achieved. Finally, we found that adding surfactants has the additional benefit of improving total kinetic energy of the ink compositions, lowering possibility of agglomerations within the ink. It also raises the nanodroplet velocity while reducing nanodroplet breakup time, which can help speed up the process of 3D printing process. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1615–1624     

Ex-vivo NMR of unprocessed tissue in water: a simplified procedure for studying intracranial neoplasms

Ex-vivo and in-vitro nuclear magnetic resonance (NMR) spectroscopy techniques have been used for studying chemical metabolites in surgically resected specimens of human neoplasms, and may provide complementary information to in-vivo whole-body magnetic-resonance spectroscopy (MRS). We describe an ex-vivo NMR in water method for measurement of water-soluble metabolites in unprocessed normal rat brain tissue and human intracranial neoplasms. The NMR spectra obtained using the method described here were comparable to those obtained using high-resolution magic-angle spinning (HRMAS) NMR methods, with good correlation in metabolite concentrations relative to creatine (r ² = 0.7635). Improved spectral resolution and baseline were noted compared to HRMAS, but macromolecule resonances were not detected. Ex-vivo NMR of unprocessed tissue in water is rapid and technically simple to perform, and has the potential to be used for direct assessment of intracranial neoplasms.     

Miscibility and specific interactions in polyacrylonitrile/ poly(p‐vinylphenol) blends

A rare miscible polyacrylonitrile (PAN) blend system is reported. PAN is miscible with poly(p‐vinylphenol) (PVPh) as shown by thermal and spectroscopic studies. A single glass transition temperature was found in each blend. Infrared spectroscopic studies showed that the hydroxyl band of PVPh and the cyano band of PAN shifted to lower frequencies upon blending, showing the existence of specific interactions between the two polymers. The involvement of cyano groups in specific interactions was further evidenced by the development of a high‐binding‐energy N1s peak in each blend from X‐ray photoelectron spectroscopic studies.     

A numerical study of the effect of free surface and water depth on the stability of wakes: use of GDQ formulation

The instability character of a wake in the presence of a free surface is examined by a recently developed GDQ (generalized differential quadrature) numerical method. It is shown that at low Froude number the wake near a free surface is convectively unstable, but when the Froude number is increased further it becomes absolutely unstable. The effect of water depth on the stability property of the wake flow is also investigated. It is found that the influence of water depth on the critical point of instability is limited to at most 20% variation in the complex frequency, while the change in temporal growth rate is also limited to about 20%. © 1997 John Wiley & Sons, Ltd.     

One-diregular subgraphs in semicomplete multipartite digraphs

The problem of finding necessary and sufficient conditions for a semicomplete multipartite digraph (SMD) to be Hamiltonian, seems to be both very interesting and difficult. Bang-Jensen, Gutin and Huang ( Discrete Math to appear) proved a sufficient condition for a SMD to be Hamiltonian. A strengthening of this condition, shown in this paper, allows us to prove the following three results. We prove that every k-strong SMD with at most k-vertices in each color class is Hamiltonian and every k-strong SMD has a cycle through any set of k vertices. These two statements were stated as conjectures by Volkmann (L. Volkmann, a talk at the second Krakw Conference of Graph Theory (1994)) and Bang-Jensen, Gutin, and Yeo (J. Bang-Jensen, G. Gutin, and A. Yeo, On k-strong and k-cyclic digraphs, submitted), respectively. We also prove that every diregular SMD is Hamiltonian, which was conjectured in a weaker form by Zhang (C.-Q. Zhang, Hamilton paths in multipartite oriented graphs, Ann Discrete Math. 41 (1989), 499–581). © 1997 John Wiley & Sons, Inc.     

The axisymmetric boundary layer beneath a Rankine-like vortex

 An experimental investigation of the three-dimensional boundary layer induced by a Rankine-like vortex with its axis normal to a stationary disk is described. The velocity field through the boundary layer was measured for Reynolds number Re (based on the tangential velocity and radius at the disk edge) ranging from 10 000 to 25 000 at various radial distances by means of a 4-beam, 2-component Laser Doppler Anemometer. Our results show that the nature of the boundary layer is affected by two factors: an inflexional instability caused by the crossflow velocity profile and a stability factor caused by the favorable pressure gradient. At lower Reynolds number, the radial pressure gradient has a very strong stabilizing effect on the boundary layer and acts to revert it to its laminar state upstream of the effusing core. At higher Re the inflexional instability caused by the crossflow velocity dominates while the stabilizing influence of the favorable pressure gradient recedes. As such, laminar reversion likely occurs closer to the effusion core. Thus, the point of laminar reversion moves closer to the effusion core as the Reynolds number is increased. Received 23 May 1996 / Accepted 29 July 1996     

Selective adhesion of intestinal epithelial cells on patterned films with amine functionalities formed by plasma enhanced chemical vapor deposition

Control of cell adhesion to surfaces is important to develop analytical tools in the areas of biomedical engineering. To control cell adhesiveness of the surface, we constructed a variety of plasma polymerized hexamethyldisiloxane (PPHMDSO) thin films deposited at the plasma power range of 10-100 W by plasma enhanced chemical vapor deposition (PECVD). The PPHMDSO film that was formed at 10 W was revealed to be resistant to cell adhesion. The resistance to cell adhesion is closely related to physicochemical properties of the film. Atomic force microscopic data show an increase in surface roughness from 0.52 nm to 0.74 nm with increasing plasma power. From Fourier transform infrared (FT-IR) absorption spectroscopy data, it was also determined that the methyl (-CH₃) peak intensity increases with increasing plasma power, whereas the hydroxyl (-OH) peak decreases. X-ray photoelectron spectroscopy data reveal an increase in C-O bonding with increasing plasma power. These results suggest that C-O bonding and hydroxyl (-OH) and methyl (-CH₃) functional groups play a critical part in cell adhesion. Furthermore, to enhance a diversity of film surface, we accumulated the patterned plasma polymerized ethylenediamine (PPEDA) thin film on the top of the PPHMDSO thin film. The PPEDA film is established to be strongly cell-adherent. This patterned two-layer film stacking method can be used to form the selectively limited cell-adhesive PPEDA spots over the adhesion-resistant surface.