Luminescence and electrification in a flow of dielectric liquids through narrow channels

Blue-violet luminescence was observed in a mineral oil, which appeared under hydrodynamic cavitation conditions in a channel orifice 1 mm in diameter in a transparent throttling device at inlet pressures higher than 2 MPa. The appearance of electric pulses when a dielectric liquid flew through a thin channel orifice was observed much earlier than luminescence arose. A device for continuously scanning electric potential along a flow without disturbing it was developed. According to the oscillograms obtained, the electric signal was high-frequency, could not be synchronized, and its separate peaks reached 1000 mV. Light emission flux decreased as the temperature of the liquid increased to 30–35°C and inlet pressure grew. The appearance of luminescence and its intensity depended on the sharpness of the entrance edge of the throttle. Studies of hydrodynamic luminescence revealed hysteresis of light emission. A mechanism of localized light emission based on an important role played by electrokinetic phenomena was suggested.     

The appearance of electrification of hydrocarbons flowing in a tube

The appearance of a substantial potential difference in a dielectric liquid (∼1000 V) flowing through a tube 6 mm in diameter was observed using metallic electrodes situated along the flow. The effect was called hydroelectric. According to the oscillograms obtained, the electric signal was high-frequency, could not be synchronized, and the potential difference between the entrance and exit of the capillary reached 200 V for positive pulses and 700 V for negative pulses. The potential difference decreased as the temperature of the liquid increased to 30–35°C and hydrostatic upthrust grew. A mechanism of the appearance of potential difference based on the predominant role played by electrokinetic phenomena was developed.     

Formation mechanism and luminescence appearance of Mn-doped zinc silicate particles synthesized in supercritical water

Luminescence appearance of Mn-doped zinc silicate (Zn₂SiO₄:Mn²⁺, ZSM) formed in supercritical water at 400 °C and 29 MPa at reaction times from 1 to 4320 min was studied in the relation to its phase formation mechanism. Appearance of luminescent ZSM from green emission by α-ZSM and yellow emission by β-ZSM occurred over the same time period during the onset of phase formation at a reaction time of 2 min. Luminescence appeared at a much lower temperature and at shorter reaction times than the conventional solid-state reaction. Needle-like-shaped α-ZSM was the most stable particle shape and phase in the supercritical water reaction environment and particles formed via two routes: a homogenous nucleation route and a heterogenous route that involves solid-state diffusion and recrystallization.     

Rheology of dilute polyelectrolyte solutions in narrow channels

The shear flow of dilute polyelectrolyte solutions bounded by either neutral or repulsive walls is modeled using a nonlinear dumbbell with conformation-dependent friction. Assuming that the configurational probability density function depends on the internal coordinates (r) and the distance of the center of mass of the molecule to the walls, coupled differential equations for the tensor moments <rr> are obtained. Coulombic repulsion between beads is considered to simulate the charge repulsion between ionized sites distributed along the backbone of a real polyelectrolyte. The repulsive interaction between the polyelectrolyte molecule and the charged walls is that of the DLVO model and the molecule is considered to be a charged sphere. Numerical solutions for the components of the tensor <rr> are worked out with the preaverage approach, and only when neutral walls considered are exact solutions obtained. Viscosity results show that in the limit of very wide channels, the corresponding viscosity in the bulk is obtained. The wall repulsion on the charged molecules produces migration of molecules towards the center of the channel resulting in a depleted layer with lower viscosity next to the walls. The calculated slip phenomenon using the method employed by Grisafi and Brunn is dependent on the beads repulsion and the shear rate. The slip velocity obtained with the Mooney method shows similarities with available experimental results for polyelectrolyte solutions. Birefringence calculations are performed in narrow and wide channels for different bead repulsions, with interesting results for both flexible and rigid molecules. Received: 26 September 1998 Accepted in revised form: 11 March 1999     

Pressure-induced transport of DNA confined in narrow capillary channels

Pressure-induced transport of double-stranded DNA (dsDNA) from 10 base pairs (bp) to 1.9 mega base pairs (Mbp) confined in a 750-nm-radius capillary was studied using a hydrodynamic chromatographic technique and four distinct length regions (rod-like, free-coiled, constant mobility, and transition regions) were observed. The transport behavior varied closely with region changes. The rod-like region consisted of DNA shorter than the persistence length (～150 bp) of dsDNA, and these molecules behaved like polymer rods. Free-coiled region consisted of DNA from ～150 bp to ～2 kilo base pairs (kbp), and the effective hydrodynamic radius R(HD) of these DNA scaled to L(0.5) (L is the DNA length in kbp), a characteristic property of freely coiled polymers. Constant mobility region consisted of DNA longer than ～100 kbp, and these DNA had a constant hydrodynamic mobility and could not be resolved. Transition region existed between free-coiled and constant mobility regions. The transport mechanism of DNA in this region was complicated, and a general empirical equation was established to relate the mobility with DNA length. Understanding of the fundamental principles of DNA transport in narrow capillary channels will be of great interest in the development of "lab-on-chip" technologies and nongel DNA separations.     

Quasi-static liquid-air drainage in narrow channels with variations in the gap

This paper studies the shape of an air bubble quasi-statically flowing in the longitudinal direction of narrow channels. Two bottom topographies are treated, i.e., linear and quadratic variations of the gap along the transverse direction. This work analyses the main characteristics of the gas-liquid interface with respect to the wedge aspect ratio. From the convergence of asymptotic, numerical and experimental analyses, we found simple dependences for the finger width and total curvature as a function of channel aspect ratio. These results provide simple and general expressions for the pressure drop needed to overcome capillary forces and push the air finger inside the channel.     

Collective behavior during the exit of a wetting liquid through a network of channels

The exit of a wetting fluid from a thin microchannel into a sudden expansion is studied experimentally. In the case of the exit from a single channel, the advancing interface converges to a parabolic shape after an initial transient, in accordance with the lubrication limit analysis of a spreading drop. The experiments are then repeated for the exit from two parallel channels. At early times, the two exiting drops behave independently and display the same evolution as a single exiting droplet, while at late times we recover a single parabolic profile. The transition between the early and late states is due to the merging of the two drops, which is associated with a sudden increase in the flow rate. This is the signature of a collective effect which acts to redistribute the fluid spatially. Finally, the experiment is generalized to the case of seven parallel channels where a cascade of two-by-two mergings is observed, indicating that local interactions dominate the dynamics which lead to the global state of the system.     

Static electrification of solid oxide in liquid metal and electrical double layer at the interface

Static electrification of a solid oxide, say a semiconducting oxide in liquid metal, is mainly due to electron transfer between two phases. Excess electrons in the liquid metal phase provided by the oxide give rise to an electrical double layer at the interface. The electrical double layer may be divided into three parts, an immobile inner layer, a compressed diffuse layer, and a flat layer extending into the bulk liquid metal. Differential potential analysis and the induced emf method were used to measure the potential of the compressed diffuse layer and the excess electron density of the flat layer, respectively. Results show that most oxides in liquid metals carry positive charges on their surfaces and the potentials of the compressed diffuse layer are in the range of 3 to 42 microV. Such a low potential implies that the diffuse layer is considerably compressed. The excess electron densities of the flat layer are on the order of 10(22) electrons/m(3) of Hg and their contributions to surface charges of oxide are in the range of 10(17) to 10(18) charges/m(2) for the oxide/mercury systems with a solid density of 0.3 wt% at room temperature.     

The flow of concentrated surfactant solutions through narrow capillaries

 The resistance of microfilters in a flow of micellar solutions indicates that the surfactant which is adsorbed in the pores forms a mobile admicelle. The flow in these admicelles can be stopped by Marangoni forces if there is a concentration gradient of surfactant across the filter. On the basis of thermodynamic concepts and experimental data it is argued that the resistance of the filters could be affected by shear-induced surfactant adsorption. To minimize the entropy production in the flow through a narrow pore the micellar solution separates into parallel fluxes of liquid through the lumen of the pore and of mobile surfactant in the flowing admicelle. Received: 14 July 1999 Accepted: 24 November 1999     

A generalized analysis of capillary flows in channels

Investigations on the motion of a fluid in capillary geometries have been extensively reported in the literature using both experimental and theoretical approaches. In this paper, the theories for capillary flow are generalized to a unified nonlinear second-order differential equation which takes the effects of the entrance, the inertial forces, and the dynamic contact angle into account. An analytical solution of the differential equation is obtained in the form of a double Dirichlet series. The readily evaluated analytical solution is compared with experimental and numerical results in the literature, which shows a good agreement. It is demonstrated that this analytical approach can be used to predict capillary flows for a wide range of fluids and parallel-plate and tube geometries in a unified manner.     

The hydrophobic acyl-chain effect in the lipid domains appearance through phospholipid bilayers

An intermolecular interaction model for selective association processes of double-chain phospholipids in bilayer lipid membranes has been proposed, analysed and solved numerically. A large variety of binary mixtures of asymmetrical double-chain phospholipids with the cross-sectional areas of the polar headgroups a₁ = 40 Ų (the first component) and a₂ = 60 Ų (the second component) have been investigated. Changing the hydrophobic acyl-chain lengths of both mixture components, we found in all cases that the self-association probability (the association of like-pairs of phospholipids) of the first component in parallel alignment of the electric dipole moments of the polar headgroups is higher than the cross-association probability (the association of cross-pairs of phospholipids) and the self-association probability of the second component. This result is in good agreement with the experimental evidence that where the cross-sectional area of the polar headgroups matches the hydrocarbon chain-packing cross-sectional area (a 2Ξ 40 Ų), lipids possess a high tendency to aggregate into well packed bilayer structures with the acyl-chains oriented perpendicularly to the bilayer plane. Our theoretical data confirm that the double-chain phospholipids may associate themselves into anti-parallel alignment of the polar headgroups (P′₂₂) as well. The hydrophobic acyl-chain effect of phospholipids may modulate the distribution of lipid domains within bilayers that have a large variety of functional roles in cellular metabolism.     

Change of the luminescence properties of charge-transfer complexes in liquid solutions

The deactivation mechanism of the excited charge-transfer complex in non-polar and polar solvents has been discussed on the basis of measured quantum yields and decay times of fluorescence of charge-transfer complexes of pyromellitic dianhydride with some methylbenzenes. It has been pointed out that great changes of electronic structure in the excited state, caused by strong excited complex—solvent interaction, are responsible for the very low fluorescence quantum yield observed in polar solvents.     

Molecular arrangements and conformations of liquid unbranched alkanes in narrow slits

Realistic, atomistic models of liquid tridecane in broad slits (>3 nm) and in narrow slits of thickness 1,2 nm and 1,0 nm have been obtained using the Monte Carlo technique. The setup of the models is such that the molecules in the slits are in equilibrium with the bulk liquid. The surfaces of the plates are modelled as two-dimensional arrays of hexagonally packed units having the same size and interaction parameters of a methylene group. The regions adjacent to the plates in slits with thickness > 3 nm are characterized by a well defined tendency to form partially ordered layer structures, while molecules at a distance from the plates larger than 1,5 nm are unperturbed. The simultaneous presence of two plates increases the tendency to form layer structures when their distance is 1,2 nm, while this tendency is almost totally destroyed when the slit is squeezed down to a thickness of 1,0 nm. This is also associated with a 10% decrease of the density in the latter slit.     

Electron trapping and luminescence mechanism in thermoluminescence of irradiated polycarbonate

Thermoluminescence of polycarbonate irradiated by electron beams was observed in order to investigate the trapping of electrons and the luminescence mechanism. The thermoluminescence glow curve is composed of three components. The peaks appear at ?150°C (α peak), ?120°C (β peak), and ?30°C (γ peak). The α peak is attributed to recombination of cations with electrons released from trapping sites formed by carbonate groups. The β peak is attributed to small amounts of impurities. The γ peak is perhaps due to untrapping of electrons from the phenoxy anion. The luminescence intensity of the α peak is linearly dependent on the absorbed dose, and that of the β peak is approximately proportional to the cube of the dose. The appearance of these peaks is presumably closely related to local molecular motions.     

Application of long-lived luminescence for detection in liquid chromatography

Summary Quenched and sensitized lanthanide luminescence as detection in liquid chromatography has been investigated. An important advantage in comparison with phosphorescence is that the long-lived luminescence as applied does not require deoxygenation of the samples. In order to obtain a high luminescence intensity Tb(III) complexes with acetylacetonate have been formed, after which indirect excitation of Tb(III) can be realized via the ligands. The potential of Tb(III) luminescence as a detection method in ion chromatography has been shown for chromate, which is an efficient quencher. Sensitizing of the Tb(III) luminescence has been applied for thiol-containing analytes. These compounds are derivatized with maleimidyl salicylic acid to complexes that sensitize the Tb(III) luminescence. From a comparison of the results obtained with normal fluorescence detection and time-resolved sensitized Tb(III) luminescence detection it has become clear that the last method has a higher sensitivity, but in particular a higher selectivity.     

Collisional deactivation mechanism of luminescence in hydrogen-loaded Ge-doped fibers

We report experimental results on the temperature and Ge-content dependencies of the decay times of the 3.1 eV emission of twofold-coordinated germaniums, excited at 3.51 eV, in both virgin and H2-loaded germanosilicate optical fibers. For T<110 K, the lifetimes are temperature invariant in the two kinds of fibers; at higher temperatures, they are progressively shortened in the H2-loaded fibers whereas they remain unaltered in the virgin fibers. On increasing the Ge content in the fiber core the lifetime decreases in the whole temperature range. We also found a direct correlation in H2-loaded samples between the dependencies on temperature of the emission lifetime and the diffusion lengths of H2 molecules in silica glass determined from earlier work. These experimental features are explained by assuming an elastic-collisional deactivation mechanism due to interaction with diffusing H2 molecules, described in terms of an Arrhenius law with activation energy approximately 64 meV that operates in competition with the normal radiative process.     

The study on the effect and mechanism of the second ligands on the luminescence properties of terbium complexes

The binary complex of Tb(III) with N-phenylanthranilic acid (N-HPA) was synthesized, and the ternary complexes were synthesized by introducing 1,10-phenanthroline (Phen), 2,2'-dipyridyl (Bipy), trioctylphosphine oxide (TPPO) as the second ligand, respectively. These complexes were characterized by infrared spectra, UV spectra and fluorescence spectra. The effect and mechanism of different second ligands on the fluorescent intensity of the terbium N-phenylanthranilic acid complexes was discussed. It showed that all the complexes exhibited ligand-sensitized green emission. The luminescence intensity increased in the sequence of Tb(N-PA)(3)Phen相似文献   

The mechanism of Raf activation through dimerization

Raf, a threonine/serine kinase in the Raf/MEK/ERK pathway, regulates cell proliferation. Raf''s full activation requires dimerization. Aberrant activation through dimerization is an important therapeutic target. Despite its clinical importance, fundamental questions, such as how the side-to-side dimerization promotes the OFF-to-ON transition of Raf''s kinase domain and how the fully activated ON-state kinase domain is stabilized in the dimer for Raf signaling, remain unanswered. Herein, we decipher an atomic-level mechanism of Raf activation through dimerization, clarifying this enigma. The mechanism reveals that the replacement of intramolecular π–π stacking by intermolecular π–π stacking at the dimer interface releases the structural constraint of the αC-helix, promoting the OFF-to-ON transition. During the transition, the inhibitory hydrophobic interactions were disrupted, making the phosphorylation sites in A-loop approach the HRD motif for cis-autophosphorylation. Once fully activated, the ON-state kinase domain can be stabilized by a newly identified functional N-terminal basic (NtB) motif in the dimer for Raf signaling. This work provides atomic level insight into critical steps in Raf activation and outlines a new venue for drug discovery against Raf dimerization.

We decipher an atomic-level mechanism of Raf activation through dimerization, revealing that the disruption of intramolecular π–π stacking at the dimer interface promotes the OFF-to-ON transition.     

Estimation of some parameters of the exchange mechanism of luminescence decay

The rates of variations of the relative yield (α_η) and decay time (α_τ) with the acceptor concentration (C_A) have been calculated in the vicinity of C_A = 0. On the basis of the equations obtained, the ratio α_η/α_τ has been found and a simple scheme of experimental data analysis proposed.     

NMR observation of the conformations and motions of polymers confined to the narrow channels of their inclusion compounds

When polymers are guests in crystalline inclusion compounds (ICs) formed with small-molecule hosts, they occupy a unique environment. In a cocrystallization process the small-molecule host forms a crystalline lattice containing long narrow channels where the guest polymer chains are included. Because of the narrow channel diameter and because neighboring channels are separated by walls formed exclusively from the small-molecule host lattice, the included polymer chains are highly extended and separated from polymer chains in other IC channels. As a consequence, polymer-IC crystals provide a unique solid state environment for the included polymer chains and serve as models useful for assessing the contributions made by the inherent behavior of individual polymer chains to the properties of ordered, bulk polymers, which can be obscured by pervasive interactions between their tightly packed polymer chains. In this paper we describe the conformations and motions of polymer chains confined to the narrow channels of the following polymer-ICs: i. polyethylene and trans-1, 4-polybutadiene in their ICs with perhydrotriphenylene, ii. polyepsilon caprolactone and its diblock and triblock copolymers with polybutadiene and poly (ethylene oxide) in their ICs with urea, and iii. nylon-6 in its ICs with alpha-, beta-, and gamma-cyclodextrins. High resolution, solid state NMR serves as both the conformational (C-13 chemical shifts) and motional (relaxation times and line shapes) probe. Comparison with identical NMR measurements performed on the bulk homo- and copolymer samples permits us to draw several conclusions regarding the relationships between the conformations and motions of polymers and their dependence on their ordered solid state environments.