Vacuum‐driven fluid manipulation by a piezoelectric diaphragm micropump for microfluidic droplet generation with a rapid system response time

Recently, we developed a convenient microfluidic droplet generation device based on vacuum‐driven fluid manipulation with a piezoelectric diaphragm micropump. In the present study built on our previous work, we investigate the influence of settings applied to the piezoelectric pump, such as peak‐to‐peak drive voltage (V_p‐p) and wave frequency, on droplet generation characteristics. Stepwise adjustments to the drive voltage in ±10‐V_p‐p increments over the range of 200?250 V_p‐p during droplet creation revealed that the droplet generation rate could be reproducibly controlled at a specific drive voltage. The droplet generation rate switched within <0.5 s after the input of a new voltage. Although the droplet generation rate depended on the drive voltage, this setting had almost no influence on droplet size. The frequency over the selected range (50?60 Hz) did not markedly influence the droplet generation rate or droplet size. We show that the current fluid manipulation system can be conveniently used for both droplet generation and for rapid droplet reading, which is required in many microfluidic‐based applications.     

D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Stochastic optimization of forward recursive functions

This note solves a finite-horizon stochastic optimization problem with forward recursive criterion through dynamic programming. The forward recursive criterion is wide; it includes additive (discounted), multiplicative (discounted risk-sensitive), minimum and terminal criteria. The basic idea is to apply invariant imbedding method for the stochastic optimization. The method incorporates recursive accumulation process into dynamics by expanding the original state space.     

Modelling of a single drop impact onto liquid film using particle method

The process of single liquid drop impact on thin liquid surface is numerically simulated with moving particle semi‐implicit method. The mathematical model involves gravity, viscosity and surface tension. The model is validated by the simulation of the experimental cases. It is found that the dynamic processes after impact are sensitive to the liquid pool depth and the initial drop velocity. In the cases that the initial drop velocity is low, the drop will be merged with the liquid pool and no big splash is seen. If the initial drop velocity is high enough, the dynamic process depends on the liquid depth. If the liquid film is very thin, a bowl‐shaped thin crown is formed immediately after the impact. The total crown subsequently expands outward and breaks into many tiny droplets. When the thickness of the liquid film increases, the direction of the liquid crown becomes normal to the surface and the crown propagates outward. It is also found that the radius of the crown is described by a square function of time: r_C = [c(t ? t₀)]^0.5. When the liquid film is thick enough, a crown and a deep cavity inside it are formed shortly after the impact. The bottom of the cavity is initially oblate and then the base grows downward to form a sharp corner and subsequently the corner moves downward. Copyright © 2004 John Wiley & Sons, Ltd.     

Facilitated sulfate transfer across the nitrobenzene-water interface as mediated by hydrogen-bonding ionophores.

Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors.