Using the meniscus in a capillary for small volume contact angle measurement in biochemical applications

The contact angle is a sensitive parameter often used to define wettability. With the increasing movement toward smaller liquid volumes in many biochemical applications, a key challenge lies in how to perform measurements in the retainer holding the reagent for rapid evaluation and limited material loss. Here, we report a simple and robust method to determine the contact angle of small volumes using the microscopic imaging of a capillary meniscus that requires only the radius and meniscus height information. An error analysis of the measurement finds the method to be highly accurate. We also uncovered that illumination delivered from the liquid end of the capillary lights up the interface, thereby facilitating the measurement.     

Modeling the liquid filling in capillary well microplates for analyte preconcentration

An attractive advantage of the capillary well microplate approach is the ability to conduct evaporative analyte preconcentration. We advance the use of hydrophobic materials for the wells which apart from reducing material loss through wetting also affords self entry into the well when the droplet size reduces below a critical value. Using Surface Evolver simulation without gravity, we find the critical diameters D(c) fitting very well with theoretical results. When simulating the critical diameters D(c)(G) with gravity included, the gravitational effect could only be ignored when the liquid volumes were small (difference of 5.7% with 5 μL of liquid), but not when the liquid volumes were large (differences of more than 22% with 50 μL of liquid). From this, we developed a modifying equation from a series of simulation results made to describe the gravitational effect. This modifying equation fitted the simulation results well in our simulation range (100°≤θ≤135° and 1 μL≤V≤200 μL). In simulating the condition of multiple wells underneath each droplet, we found that having more holes did not alter the critical diameters significantly. Consequently, the modifying relation should also generally express the critical diameter for multiple wells under a droplet.     

Selenium Blue-α and -β: turning on the fluorescence of a pyrenyl fluorophore via oxidative cleavage of the Se-C bond by reactive oxygen species

Rapid oxidation of nonfluorescent pyrenyl-CH₂SeAr (Ar = o-nitrophenyl) by hypochlorite yielded pyrenyl-CH₂Cl and pyrenyl-CH₂OH and turns on blue fluorescence, while slow oxidation of pyrenyl-CH₂SeAr with excess H₂O₂ leads to pyrenyl-CHO which emits a bluish-green fluorescence. The homolog, pyrenyl-CH₂CH₂SeAr′ (Ar′ = o-nitrophenyl) reacts slower with H₂O₂ and ClO⁻ giving the same product, vinyl pyrene.     

Manifold dynamic non-covalent interactions for steering molecular assembly and cyclization

Deciphering rich non-covalent interactions that govern many chemical and biological processes is crucial for the design of drugs and controlling molecular assemblies and their chemical transformations. However, real-space characterization of these weak interactions in complex molecular architectures at the single bond level has been a longstanding challenge. Here, we employed bond-resolved scanning probe microscopy combined with an exhaustive structural search algorithm and quantum chemistry calculations to elucidate multiple non-covalent interactions that control the cohesive molecular clustering of well-designed precursor molecules and their chemical reactions. The presence of two flexible bromo-triphenyl moieties in the precursor leads to the assembly of distinct non-planar dimer and trimer clusters by manifold non-covalent interactions, including hydrogen bonding, halogen bonding, C–H⋯π and lone pair⋯π interactions. The dynamic nature of weak interactions allows for transforming dimers into energetically more favourable trimers as molecular density increases. The formation of trimers also facilitates thermally-triggered intermolecular Ullmann coupling reactions, while the disassembly of dimers favours intramolecular cyclization, as evidenced by bond-resolved imaging of metalorganic intermediates and final products. The richness of manifold non-covalent interactions offers unprecedented opportunities for controlling the assembly of complex molecular architectures and steering on-surface synthesis of quantum nanostructures.

A real-space characterization of dynamic non-covalent interactions in molecular assemblies and chemical reactions at the atomic bond level.     

A new gradient method via quasi-Cauchy relation which guarantees descent

We propose a new monotone algorithm for unconstrained optimization in the frame of Barzilai and Borwein (BB) method and analyze the convergence properties of this new descent method. Motivated by the fact that BB method does not guarantee descent in the objective function at each iteration, but performs better than the steepest descent method, we therefore attempt to find stepsize formula which enables us to approximate the Hessian based on the Quasi-Cauchy equation and possess monotone property in each iteration. Practical insights on the effectiveness of the proposed techniques are given by a numerical comparison with the BB method.     

Measurement of the K0 charge radius and a CP-violating asymmetry and a search for CP-violating E1 direct photon emission in the rare decay KL--> pi+ pi- e+ e-

Using the complete KTeV data set of 5,241 candidate K(L)--> pi(+) pi(-) e(+) e(-) decays (including an estimated background of 204 +/- 14 events), we have measured the coupling g(CR)= 0.163 +/- 0.0149(stat) +/- 0.023(syst) of the CP conserving charge radius process and from it determined a K(0) charge radius of = [-0.077 +/- 0.007(stat) +/- 0.011(syst)]fm(2). We have determined a first experimental upper limit of 0.04 (90% C.L.) /g(e1)/ / /g(M1)/ of the couplings for the E1 and M1 direct photon emission processes. We also report the measurement of /g(M1)/ including a vector form factor /g(M1)/(1 + (a(1)/a(2))/((M(2)(p)-(M(2)(k))= 2M(K)E(gamma*)), where vector /g(M1)/= 1.11+/- 0.12(stat) +/- 0.08(syst) and a(1)/a(2) = [-0.744 +/- 0.027(stat) +/- 0.032(syst)] GeV(2)/c(2). Finally, a CP-violating asymmetry of [13.6 +/- 1.4(stat) +/- 1.5(syst)]% in the CP and T odd angle phi between the decay planes of the e(+) e(-) and pi(+) pi(-) pairs in the K(L) center of mass is reported.     

Noise reduction in tunnels by hard rough surfaces

This paper examines the feasibility of using two-dimensional hard rough surfaces to reduce noise levels in traffic tunnels with perfectly reflecting boundaries. First, the Twersky boss model is used to estimate the acoustic impedance of a hard rough surface. Second, an image source model is then used to compute the propagation of sound in a long rectangular enclosure with finite impedance. The total sound fields are calculated by summing the contributions from all image sources coherently. Two model tunnels are built to validate the proposed model experimentally. Finally, a case study for a realistic geometrical configuration is presented to explore the use of hard rough surfaces for reducing traffic noise in a tunnel which is constructed with hard boundaries.     

Reentrant isotropic phase in a discotic liquid crystal mixture

We have used X-ray diffraction and optical microscopy to study binary mixtures of 2,3,7,8,12,13-hexa-n-tetradecanoyloxy- and 2,3,7,8,12,13-hexa(4-n-undecyloxybenzoyloxy) truxenes. Our measurements confirm the existence of a reentrant isotropic phase, which is however always preceded by a mixed phase region rather than by a pure columnar phase. The nematic N_D phase displays an anomalously negative thermal expansion coefficient. We speculate on mechanisms for reentrancy in discotic mesogens.