Mesoscopic Modeling of Capillarity-Induced Two-Phase Transport in a Microfluidic Porous Structure

Mesoscopic modeling at the pore scale offers great promise in exploring the underlying structure transport performance of flow through porous media. The present work studies the fluid flow subjected to capillarity-induced resonance in porous media characterized by different porous structure and wettability. The effects of porosity and wettability on the displacement behavior of the fluid flow through porous media are discussed. The results are presented in the form of temporal evolution of percentage saturation and displacement of the fluid front through porous media. The present study reveals that the vibration in the form of acoustic excitation could be significant in the mobilization of fluid through the porous media. The dependence of displacement of the fluid on physicochemical parameters like wettability of the surface, frequency along with the porosity is analyzed. It was observed that the mean displacement of the fluid is more in the case of invading fluid with wetting phase where the driving force strength is not so dominant.     

Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

A Continuous Transition Between Quantum and Classical Mechanics. II

Examples are worked out using a new equation proposed in the previous paper to show that it has new physical predictions for mesoscopic systems.     

Equivariant Spectral Triples on the Quantum SU(2) Group

We characterize all equivariant odd spectral triples for the quantum SU(2) group acting on its L ₂-space and having a nontrivial Chern character. It is shown that the dimension of an equivariant spectral triple is at least three, and given any element of the K-homology group of SU_q(2), there is an equivariant odd spectral triple of dimension 3 inducing that element. The method employed to get equivariant spectral triples in the quantum case is then used for classical SU(2), and we prove that for p < 4, there does not exist any equivariant spectral triple with nontrivial K-homology class and dimension p acting on the L ₂-space.The first author would like to acknowledge support from the National Board of Higher Mathematics, India.     

On the dispersion of a solute in oscillating flow of a non-Newtonian fluid in a channel

The paper presents an exact analysis of the dispersion of an immiscible solute in a non-Newtonian fluid (known as an incompressible second-order fluid which shows viscoelastic behaviour) flowing slowly in a parallel plate channel in the presence of a periodic pressure gradient. Using a generalized dispersion model which is valid for all times after the solute injection, the diffusion coefficients K _i (τ)(i=1,2,3,…) are obtained as functions of time τ in the case when the initial solute distribution is in the form of a slug of finite extent. The analysis leads to the novel result that K ₂(τ) (which is a measure of the longitudinal dispersion coefficient of the solute) has a steady part S in addition to a fluctuating part D ₂(τ) due to the pulsatility of the flow. It is found that S decreases with increase in the viscoelastic parameter M for given values of the amplitude λ and frequency ω of the pressure pulsation. On the other hand, it is found that at a fixed instant τ, the amplitude of D ₂(τ) increases with increase in M for given values of λ and ω. Further it is shown that at a given instant τ, the amplitude of D ₂(τ) decreases with increase in ω for given λ and M and the profile for D ₂(τ) becomes progressively flatter with increase in ω. Finally the axial distribution of the average concentration θ _m of the solute over the channel cross-section is determined at different instants after the solute injection for several values of M, λ and ω. The present study is likely to have important bearing on the problem of dispersion of tracers in blood flow through arteries.     

Simultaneous Pseudo-Timestepping for PDE-Model Based Optimization Problems

In this paper we present a new method for the solution of optimization problems with PDE constraints. It is based on simultaneous pseudo-time stepping for evolution equations. The new method can be viewed as a continuous reduced SQP method in the sense that it uses a preconditioner derived from that method. The reduced Hessian in the preconditioner is approximated by a pseudo-differential operator, whose symbol can be investigated analytically. We apply our method to a boundary control model problem. The new optimization method needs 3.2-times the overall computational effort of the solution of simulation problem alone.     

Characterization of some essential oils and their key components: Thermoanalytical techniques

The present study was aimed at determining the kinetics of evaporation and establishing vapor pressure curves for both single and multi-component systems by thermogravimetry (TG) and differential scanning calorimetry (DSC). Essential oils (e.g. lavender oil, orange oil, clove oil and eucalyptus oil, etc.) are typically multi-component systems consisting of various volatile pure components (e.g. linalyl acetate, limonene, cinnamaldehyde, etc.) which resemble single component systems. In this study linalyl acetate was taken as the calibration compound for TG. The vapor pressure curves for the pure substances were plotted using TG and vapor pressure plots for clove oil and eucalyptus oil were constructed using DSC. The thermodynamic and kinetic parameters of the pure compounds were compared to that of the multi-component systems to quantitatively and qualitatively measure the influence of different compounds on each other. The k-value from the vapor pressure data for linalyl acetate was calculated as 112006 Pa kg^0.5mol^0.5s^-1 m^-2 K^-0.5. The vapor pressure values were used to determine the Antoine constants using the SPSS 10.0 software.This revised version was published online in November 2005 with corrections to the Cover Date.     

Self-assembled metallasupramolecular cages towards light harvesting systems for oxidative cyclization

Designing artificial light harvesting systems with the ability to utilize the output energy for fruitful application in aqueous medium is an intriguing topic for the development of clean and sustainable energy. We report here facile synthesis of three prismatic molecular cages as imminent supramolecular optoelectronic materials via two-component coordination-driven self-assembly of a new tetra-imidazole donor (L) in combination with 180°/120° di-platinum(ii) acceptors. Self-assembly of 180° trans-Pt(ii) acceptors A1 and A2 with L leads to the formation of cages Pt₄L₂(1a) and Pt₈L₂(2a) respectively, while 120°-Pt(ii) acceptor A3 with L gives the Pt₈L₂(3a) metallacage. PF₆⁻ analogues (1b, 2b and 3b) of the metallacages possess a high molar extinction coefficient and large Stokes shift. 1b–3b are weakly emissive in dilute solution but showed aggregation induced emission (AIE) in a water/MeCN mixture as well as in the solid state. AIE active 2b and 3b in aqueous (90% water/MeCN mixture) medium act as donors for fabricating artificial light harvesting systems via Förster resonance energy transfer (FRET) with organic dye rhodamine-B (RhB) with high energy efficiency and good antenna effect. The metallacages 2b and 3b represent an interesting platform to fabricate new generation supramolecular aqueous light harvesting systems with high antenna effect. Finally, the harvested energy of the LHSs (2b + RhB) and (3b + RhB) was utilized successfully for efficient visible light induced photo-oxidative cross coupling cyclization of N,N-dimethylaniline (4) with a series of N-alkyl/aryl maleimides (5) in aqueous acetonitrile with dramatic enhancement in yields compared to the reactions with RhB or cages alone.

Synthesis of Pt(ii) based metallacages as aggregation induced emissive supramolecular architectures for fabricating artificial light harvesting systems for cross coupling cyclization under visible light is achieved.     

A Two‐Dimensional Coordination Compound as a Zinc Ion Selective Luminescent Probe for Biological Applications

A 2D coordination compound {[Cu₂(HL)(N₃)]?ClO₄}_∞ ( 1 ; H₃L=2,6‐bis(hydroxyethyliminoethyl)‐4‐methyl phenol) was synthesized and characterized by single‐crystal X‐ray diffraction to be a polymer in the crystalline state. Each [Cu₂(HL)(N₃)]⁺ species is connected to its adjacent unit by a bridging alkoxide oxygen atom of the ligand to form a helical propagation along the crystallographic a axis. The adjacent helical frameworks are connected by a ligand alcoholic oxygen atom along the crystallographic b axis to produce pleated 2D sheets. In solution, 1 dissociates into [Cu₂(HL)₂(H₃L)]?2H₂O ( 2 ); the monomer displays high selectivity for Zn²⁺ and can be used in HEPES buffer (pH 7.4) as a zinc ion selective luminescent probe for biological application. The system shows a nearly 19‐fold Zn²⁺‐selective chelation‐enhanced fluorescence response in the working buffer. Application of 2 to cultured living cells (B16F10 mouse melanoma and A375 human melanoma) and rat hippocampal slices was also studied by fluorescence microscopy.     

Conformational effects on vibronic spectra and excited state dynamics of 3-fluorobenzoic acid dimer

Two conformational isomers of 3-fluorobenzoic acid dimer (3-FBA(2)) have been identified in a supersonic jet expansion by use of laser-induced fluorescence excitation (FE), UV-UV hole-burning, and dispersed fluorescence (DF) spectroscopic methods. In the FE spectrum, the S(1) origins of the two isomeric species appear at a frequency gap of only 24 cm(-1), and the vibronic intensities of the redshifted dimer (dimer I) are about two times weaker than those of dimer II. However, ab initio quantum chemistry calculations at the MP2/6-31G(**) level of theory predict that all the isomeric species of 3-FBA(2) have almost the same binding energy (approximately 17 kcal/mol) in the ground state. Furthermore, unlike benzoic acid dimer, the present system shows intense activity for a low-frequency mode in both the FE and DF spectra. With the aid of DFT (B3LYP/6-311G(**)) predicted normal mode frequencies, we have assigned the mode to the in-plane gear (cogwheel) vibration of the cyclic hydrogen-bonded frame of the dimer. The Franck-Condon profiles for vibronic excitation of the mode indicate that the distortion of the cyclic hydrogen bond frame as a result of S(1)<--S(0) excitation is larger for dimer I than dimer II. Moreover, the fluorescence lifetime at the S(1) zero-point level of the former is also significantly smaller than the latter. Using the predictions of configuration interaction singles calculations, we have proposed that the spectral and dynamical differences between the two isomeric species observed in this study are manifestations of the different characteristics of their S(1) surfaces. By measuring FE, DF, and hole-burning spectra of a mixed dimer between 3-fluobenzoic acid and benzoic acid we have shown that the isomeric features in the homodimer spectra are due to two locally excited rotamers of the 3-fluorobenzoic acid moiety.