Reversing selectivity of bambusuril macrocycles toward inorganic anions by installing spacious substituents on their portals.

Two chiral bambusurils, which are diastereomers to each other, show remarkable differences in their binding affinity and selectivity toward inorganic anions as determined by isothermal titration calorimetry. These differences are explained by quantum-chemical calculations.

Utilizing Binary Phase Segregation and Extrusion to Enhance the Electronic Properties of Graphene Nanocomposites.

Our goal in this study is to incorporate graphene nanoplatelets (GNPs) in a polymer blend of poly(lactic acid) (PLA) and isotactic polypropylene (iPP) to facilitate the dispersion of GNPs and use the morphology of phase segregation to create a pathway for concentrating GNPs to achieve percolation with lower GNP concentration. Investigating the interfacial properties between PLA/GNPs and iPP/GNPs, we noticed that iPP has a lower contact angle on GNPs compared to PLA on GNPs. This showed a great potential that the GNP are easily confined in iPP rather than in PLA domains or at the PLA/PP interfaces.

Microfluidic delivery of cutting enzymes for fragmentation of surface-adsorbed DNA molecules.

We describe a method for fragmenting, in-situ, surface-adsorbed and immobilized DNAs on polymethylmethacrylate(PMMA)-coated silicon substrates using microfluidic delivery of the cutting enzyme DNase I. Soft lithography is used to produce silicone elastomer (Sylgard 184) gratings which form microfluidic channels for delivery of the enzyme. Bovine serum albumin (BSA) is used to reduce DNase I adsorption to the walls of the microchannels and enable diffusion of the cutting enzyme to a distance of 10mm.

Synthesis of Enantiomerically Pure Bambus[6]urils Utilizing Orthogonal Protection of Glycolurils.

A general strategy for the synthesis of 2,4'-disubstituted glycoluril enantiomers on a multigram scale using orthogonal protection is reported. The use of these glycolurils is demonstrated in the synthesis of enantiomerically pure bambus[6]uril macrocycles. Moreover, the deprotection of ()-1-phenylethyl substituents on the macrocycle was achieved, opening access to various chiral bambus[6]urils post-macrocyclization modification strategy.

Highly Efficient and Selective Recognition of Dicyanoaurate(I) by a Bambusuril Macrocycle in Water.

Dicyanoaurate(I) anion, [Au(CN) ] , plays a central role in the current industrial production of gold, as its extraction from crude ore samples represents the most money-consuming step. Herein, we present the strongest host-guest recognition of dicyanoaurate anion using the bambusuril receptor in water, a highly competitive solvent. The micromolar stability of such a complex facilitated the up to date most efficient supramolecular stripping of dicyanoaurate from activated carbon at ambient temperature.

Monofunctionalized Fluorinated Bambusurils and Their Conjugates for Anion Transport and Extraction.

Bambusurils are macrocyclic molecules that are known for their high binding affinity and selectivity toward anions. Here, we present the preparation of two bambusurils bearing fluorinated substituents and one carboxylic function. These monofunctionalized bambusurils were conjugated with crown ether and cholesterol units.

Bambusuril Macrocycles as Mediators of Supramolecular Interactions: Application to the Europium Cage Helicate.

Herein, it is shown how bambusurils can be used for tuning and/or characterizing supramolecular systems. Indeed, the addition of bambusurils as anion scavengers to metal-mediated self-assemblies allows manipulation of the subtle equilibria in the given system. This is demonstrated for the case of the tetranuclear europium helical cage, which is well suited to different applications.

Functionalized Chiral Bambusurils: Synthesis and Host-Guest Interactions with Chiral Carboxylates.

Bambusurils are a class of macrocyclic anion receptors that exhibit notable anion recognition properties, able to bind various inorganic anions as well the carboxylates or sulfonates. Recently, we reported enantioselective recognition of chiral carboxylates using non-functionalized chiral bambusuril derivatives. Herein, we report the synthesis and host-guest properties of two new representatives of chiral bambusuril macrocycles bearing ester functional groups, differing by the substituents attached to their portals.

Chiral Bambusurils for Enantioselective Recognition of Carboxylate Anion Guests.

Synthesis of the first enantiomerically pure chiral bambusurils is reported. The bambusurils were prepared on the gram scale without using any chromatography techniques. The bambusurils formed supramolecular complexes with all tested chiral carboxylates including amino acids and drug molecules with the enantioselectivity ranging from 1.

Discrimination of Adsorbed Double-Stranded and Single-Stranded DNA Molecules on Surfaces by Fluorescence Emission Spectroscopy Using Acridine Orange Dye.

A sensitive and straightforward method for discriminating between surface-adsorbed double-stranded DNA (dsDNA) and single-stranded DNA (ssDNA), based on analysis of the fluorescence emission spectra of DNAs dyed with the metachromatic dye acridine orange, has been developed. Since the degree of discrimination between dsDNA and ssDNA is dependent on dye-base ratio (as has been shown in early studies of DNAs in solution), a specific, reproducible protocol for obtaining good ss-ds discrimination was needed. We studied the emission spectra for DNAs dyed in-situ on two different surfaces, polymethylmethacrylate and poly-l-lysine, using acridine orange solutions of varying concentrations in either 2-(N-morpholino)ethanesulfonic acid (MES) or Tris-Borate EDTA (TBE) buffers.

Dewetting of the three-phase contact line on solids.

Liquid adsorption on a substrate has great applications in inkjet printing as well as micro/nano fabrication. In this letter, we focus on obtaining a better understanding of the pinning-dewetting phenomenon through solubility measurements during droplet evaporation. The physical adsorption/penetration of liquid on the substrate material is considered to be responsible for the pinning of the three-phase contact line.

Imaging and estimating the surface heterogeneity on a droplet containing cosolvents.

Cosolvents have numerous applications in many industries as well as scientific research. The shortage in the knowledge of the structures in a cosolvent system is significant. In this work, we display the spatial as well as the kinetic distribution of the cosolvents using droplets as paradigms.

The effect of organo clay and adsorbed FeO(3) nanoparticles on cells cultured on Ethylene Vinyl Acetate substrates and fibers.

Nanocomposites of Ethylene Vinyl Acetate (EVA 260) with Cloisite 20A organo clay and Cloisite 20A organo clay impregnated with Fe(CO)(5) were produced in a twin-screw extruder. Dynamic mechanical analysis (DMA) measurements indicated that the moduli increased monotonically for the Cloisite, up to a concentration of 10%, after which the modulus decreased. Adult human dermal fibroblasts (AHDF) were plated on these surfaces and the cell growth was found to be maximal on the nanocomposites containing 10% Cloisite.

Determination of three characteristic regimes of weakly charged polyelectrolytes monolayers.

We have demonstrated that monolayer films of randomly charged polystyrene sulfonated acid (PSSA) can be produced by the Langmuir technique, and observed the micro-domain structures, produced by the phase separation of electrostatically charged moieties and the hydrophobic moieties. Using atomic force microscopy and Langmuir isotherm, we found three specific regimes for the polyelectrolytes with various degrees of sulfonation (4-35%); very low charged PSSA (4-5%) in the hydrophobic regime, moderately charged PSSA (6-16%) which possessed a well-balanced nature between electrostatic and the hydrophobic interactions, and strongly amphiphilic nature of PSSA (6-16%) in the ionomer regime. Finally, we could categorize PSSA 35% in the polyelectrolyte regime, due to the dominance of the electrostatic interactions over the hydrophobic interactions.

A potentiometric protein sensor built with surface molecular imprinting method.

Surface molecular imprinting, as compared to molecular imprinted bulk polymers, has the advantages of higher re-occupation percentage of the reception sites, fast response, integration of sensing element and transducer, etc. In this study, a potentiometric protein sensor was developed based on the surface molecular imprinting technique. Using the self-assembled monolayers of alkanethiol with hydroxyl terminal groups as the matrix material, and target protein molecules as the template, the sensing layer was created on the surface of the gold-coated silicon chip-an electrochemical transducer.

DNA migration and separation on surfaces with a microscale dielectrophoretic trap array.

We studied the surface migration of DNA chains driven by a dc electric field across localized dielectrophoretic traps. By adjusting the length scale of the trap array, separation of a selected band of DNA was accomplished with a scaling exponent between mobility and number of base pairs similar to that obtained in capillary electrophoresis. We then provided a model, which predicts the trapping and extension of DNA chains at a dielectrophoretic trap responsible for the surface mobility and separation.

Adverse effects of citrate/gold nanoparticles on human dermal fibroblasts.

Nanoscale engineering is one of the most dynamically growing areas at the interface between electronics, physics, biology, and medicine. As there are no safety regulations yet, concerns about future health problems are rising. We investigated the effects of citrate/gold nanoparticles at different concentrations and exposure times on human dermal fibroblasts.

Comparison of decanethiolate gold nanoparticles synthesized by one-phase and two-phase methods.

We investigated the differences between the decanethiolate gold nanoparticles synthesized by two different routes: one-phase and two-phase methods. Their properties were compared in bulk and at the air-water interface by transmission electron microscopy (TEM), X-ray reflectivity (XR), extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction (XRD), thermal gravimetric analysis (TGA), time-of-flight secondary-ion mass spectrometry (TOF-SIMS), electron paramagnetic resonance (EPR), and Langmuir-Blodgett technique. The mean nanoparticles sizes obtained by EXAFS and XRD were found to be smaller than those by the TEM measurements.

Dual-syringe reactive electrospinning of cross-linked hyaluronic acid hydrogel nanofibers for tissue engineering applications.

A facile fabrication of a cross-linked hyaluronic acid (HA) hydrogel nanofibers by a reactive electrospinning method is described. A thiolated HA derivative, 3,3'-dithiobis(propanoic dihydrazide)-modified HA (HA-DTPH), and poly(ethylene glycol) diacrylate (PEGDA) are selected as the cross-linking system. The cross-linking reaction occurs simultaneously during the electrospinning process using a dual-syringe mixing technique.

Factors controlling the drop evaporation constant.

In this paper, we discuss the factors affecting drop evaporation. We found that the droplet morphology at a specific temperature was controlled by the physical properties of the liquid itself, such as the molecular weight, density, diffusion coefficient in air, and heat of vaporization. Two processes are included in drop evaporation: diffusion of liquid molecules into the air (diffusion part) and flow of the liquid molecules from inside the drop to the free outer shell liquid layer within the liquid-vapor interface (evaporation part).

Separation of DNA with different configurations on flat and nanopatterned surfaces.

We demonstrate that electrophoresis on a flat Si substrate is an effective method in separation of DNA with different configurations, e.g., linear, supercoiled, and relaxed or DNA of different length, e.

Drying of DNA droplets.

The evaporation kinetics of droplets containing DNA was studied, as a function of DNA concentration. Drops containing very low DNA concentrations dried by maintaining a constant base, whereas those with high concentration dried with a constant contact angle. To understand this phenomenon, the distribution of the DNA inside the droplet was measured using confocal microscopy.