Evaporative Preconcentration of Fluorescent Protein Samples in Capillary Based Microplates

The preconcentration of analytes is important in biochemical analysis as it offers the ability to detect for trace species, and increase signal-to-noise ratios when using optical sensing on fluorophores. A strong advantage of the evaporation technique lies in its ability to operate without the need of any energy source; albeit major challenges exist on how to increase the surface area exposure to air for heightened evaporation, ensure no further increases once specified analyte concentrations have been achieved, and not needing any intervening membranes. We demonstrate here that the droplet creation and retraction approach in capillary based microplates offers such abilities whilst at the same time facilitating mixing.     

A Discrete Lagrangian-Based Global-Search Method for Solving Satisfiability Problems

Satisfiability is a class of NP-complete problems that model a wide range of real-world applications. These problems are difficult to solve because they have many local minima in their search space, often trapping greedy search methods that utilize some form of descent. In this paper, we propose a new discrete Lagrange-multiplier-based global-search method (DLM) for solving satisfiability problems. We derive new approaches for applying Lagrangian methods in discrete space, we show that an equilibrium is reached when a feasible assignment to the original problem is found and present heuristic algorithms to look for equilibrium points. Our method and analysis provides a theoretical foundation and generalization of local search schemes that optimize the objective alone and penalty-based schemes that optimize the constraints alone. In contrast to local search methods that restart from a new starting point when a search reaches a local trap, the Lagrange multipliers in DLM provide a force to lead the search out of a local minimum and move it in the direction provided by the Lagrange multipliers. In contrast to penalty-based schemes that rely only on the weights of violated constraints to escape from local minima, DLM also uses the value of an objective function (in this case the number of violated constraints) to provide further guidance. The dynamic shift in emphasis between the objective and the constraints, depending on their relative values, is the key of Lagrangian methods. One of the major advantages of DLM is that it has very few algorithmic parameters to be tuned by users. Besides the search procedure can be made deterministic and the results reproducible. We demonstrate our method by applying it to solve an extensive set of benchmark problems archived in DIMACS of Rutgers University. DLM often performs better than the best existing methods and can achieve an order-of-magnitude speed-up for some problems.     

Dual Esterase‐ and Steroid‐Responsive Energy Transfer Modulation of Ruthenium(II) and Rhenium(I) Complex Functionalized Gold Nanoparticles

A number of adamantane‐containing ruthenium(II) and rhenium(I) complexes have been synthesized, characterized, and noncovalently functionalized with β‐cyclodextrin‐capped gold nanoparticles (β‐CD–GNPs) through the host–guest interaction between cyclodextrin and adamantane. The resultant nanoconjugates have been characterized by transmission electron microscopy (TEM), energy‐dispersive X‐ray analysis (EDX), and 2D ROESY ¹H NMR experiments. The Förster resonance energy transfer (FRET) properties of the nanoconjugates can be modulated by both esterase‐accelerated hydrolysis and competitive displacement of steroid, by monitoring the emission intensity and luminescence lifetime. The FRET efficiencies are found to vary with the nature of the chromophores and the length of the spacer between the transition metal complexes and the GNPs. This work constitutes a “proof‐of‐principle” assay method for the dual‐functional detection of important classes of biomolecules, such as enzymes and steroids.     

Cleavage of a PN Bond in a Urea‐Containing (Ph2P(R)PPh2)‐Bridged Dinuclear Gold(I) Thiolate Complex by Fluoride and a Mechanistic Insight

A urea‐containing, (Ph₂P(R)PPh₂)‐bridged, dinuclear, gold(I) thiolate complex, [Au₂{Ph₂PN(C₆H₄OMe‐4)PPh₂}(SC₆H₄NHCONHC₆H₅)₂] ( 1 ) was designed and synthesized and its photophysical and anion recognition properties studied. The results show that 1 has a high selectivity toward F^?. Upon addition of F^?, the yellow solution was decolorized, and drastic changes of emission and ¹H and ³¹P{¹H} NMR signals were observed. Interestingly, these changes are attributed to fluoride‐assisted P?N bond hydrolysis, instead of the expected hydrogen‐bonding interactions with the urea receptor. Similar changes were observed for two other basic anions, AcO^? and H₂PO₄^?, but to a much lesser extent; and these anions were found to bind to the urea receptor at the same time. On the other hand, Cl^? was found to only bind to the urea moiety through hydrogen‐bonding interactions. Further studies with the control complex [Au₂{Ph₂PN(C₆H₄OMe‐4)PPh₂}Cl₂] ( 2 ) indicate that F^? assists the hydrolysis process via cleavage of the P?N bond. DFT calculations were performed to study the reaction mechanism for the fluoride‐assisted P?N bond hydrolysis of 2 ; these provide a better insight into the role of fluoride in the hydrolysis.     

Eluent-Induced Separation of Inorganic Cations in Capillary Liquid Chromatography with Contactless Conductivity Detector

A non-suppressed contactless conductivity detector has been used as a capillary detector in a capillary ion chromatograph, combining a reversed-phase C30 column permanently modified with ionic surfactant. The C30 column (100 × 0.32 mm. id) was modified with sodium dodecyl sulfate (SDS) for the separation of inorganic cations. Monovalent cations could be separated by the proposed system, in which methanesulfonic acid (MSA) and SDS were employed as the mobile phase component, but divalent cations could not be eluted under this condition. As for the case of SDS used as the eluent, an H⁺-cation-exchange column was placed before the sample injector to convert the Na⁺ from the eluent into H⁺, and when the mixture of MSA and dodecyl sulfuric acid was used as the eluent, the retention of cations was improved and baseline separation of the cations was achieved within 23 min. The effect of the eluent composition on the retention behavior of inorganic cations was investigated. The repeatability of retention time and peak height varied from 0.39 to 0.58 and 2.21 to 3.25 % as relative standard deviation, respectively.

     

Increased stability and size of a bubble on a superhydrophobic surface

Computational and theoretical models of millimeter-sized bubbles placed on upright hydrophobic and superhydrophobic surfaces are compared with experimental data here. Although the experimental data for a hydrophobic surface corroborated the computational and theoretical data, the case of a superhydrophobic surface showed the bubbles to be able to contain significantly larger volumes than predicted. This is attributed to the greater ability of the bubble contact line to advance compared with its tendency to detach from the surface because of buoyancy. We surmise that a static model therefore describes only an unstable equilibrium for these bubbles, which unless heavily isolated from external influences are more likely to assume a larger stable size.