Novel adsorbent hollow fibres for oxygen concentration

The research examined the development of adsorbent hollow fibres as a low pressure drop structure for the production of oxygen-enriched air. The potential benefits of using a low pressure drop flexible adsorbent structure with molecular sieving properties over a bed packed with pellets include a low attrition resistance which could extend the life of the adsorbent structure. Highly macroporous, highly adsorbent loaded (up to 90 wt%) fibres were produced. By increasing adsorbent density, the separative performance and nitrogen loading were improved. The separative performance of the adsorbent fibre was found to be slightly inferior to that of the bed of smaller 0.4–0.8 mm beads, as the diffusion path length was longer in the fibres and caused increased mass transfer resistances within the macroporous structure. The pressure drop through the fibre was found to be 40 to 70 times lower than that through an equivalent packed bed of 0.4–0.8 mm beads. This experimental feasibility study has demonstrated that the novel zeolite fibre configuration shows good potential for the production of oxygen-enriched air in a low energy, short cycle time, pressure swing process. The challenges of improving the performance of the adsorbent fibres and their operating parameters are described.     

Brownian coagulation at high concentration

Particle growth by Brownian coagulation at high concentration in the continuum regime is investigated by solving the Langevin dynamics (LD) equations for each particle trajectory of polydisperse suspensions. By monitoring the LD attainment of the self-preserving size distribution (SPSD), it is shown that the classic Smoluchowski collision frequency function is accurate for dilute particle volume fractions, phis, below 0.1%. At higher phis, coagulation is about 4 and 10 times faster than for the classic theory at phis = 10 and 20%, respectively. For complete particle coalescence upon collision, SPSDs develop even in highly concentrated suspensions (up to phis = 35%), as with dilute ones, but are broadened with increasing phis. At high particle concentration, an overall coagulation rate is proposed that reduces to the classic one at low concentration. Detailed collision frequency functions are also obtained at various phis values. Fractal-like agglomerates undergoing coagulation at constant fractal dimension attain an SPSD only temporarily because their effective volume fraction continuously increases, approaching gelation in the absence of restructuring or fragmentation.     

Solvent-exfoliated graphene at extremely high concentration

We describe three related methods to disperse graphene in solvents with concentrations from 2 to 63 mg/mL. Simply sonicating graphite in N-methyl-2-pyrrolidinone, followed by centrifugation, gives dispersed graphene at concentrations of up to 2 mg/mL. Filtration of a sonicated but uncentrifuged dispersion gives a partially exfoliated powder that can be redispersed at concentrations of up to 20 mg/mL. However, this process can be significantly improved by removing any unexfolaited graphite from the starting dispersion by centrifugation. The centrifuged dispersion can be filtered to give a powder of exfoliated few-layer graphene. This powder can be redispersed at concentrations of at least 63 mg/mL. The dispersed flakes are ~1 μm long and ~3 to 4 layers thick on average. Although some sedimentation occurs, ~26-28 mg/mL of the dispersed graphene appears to be indefinitely stable.     

Improved MALDI-TOF imaging yields increased protein signals at high molecular mass

Matrix assisted laser desorption ionization (MALDI) mass spectrum images are created from an array of mass spectra collected over a tissue surface. We have increased the mass range of proteins that can be detected in tissue sections from kidneys, heart, lung and brain of different rodent species by a modification of the sandwich technique, which involves co-crystallizing matrix with analyte. A tissue section is placed upon a drop of sinapinic acid matrix dissolved in 90% ethanol and 0.5% Triton X-100. Once the matrix has dried, a seed layer of sinapinic crystals is added as a dispersion in xylene. Additional layers of sinapinic acid are added as solutions in 90% ethanol followed by 50% acetonitrile. Numerous peaks with signal to noise ratio of four or greater are observed between 25 kDa to 50 kDa. This represents approximately 10 times as many peaks as are detected using traditional matrix spotting and spraying.     

Fabrication of gold microtubes and microwires in high aspect ratio capillary arrays

In this communication, we describe the sequential deposition of materials in capillaries as a means to produce self-assembled three-dimensional gold microtubes, hollow gold microwires, and microtube and microwire arrays with unprecedented aspect ratios. The initial application of this technique is the fabrication of an array of microwires within a silica capillary array. The physical characteristics of these microwires are characterized via SEM, electrochemistry, and electrogenerated chemiluminescence emission.     

Novel one-pot route to monodisperse thermosensitive hollow microcapsules in a microfluidic system

We present a simple one-pot synthetic approach for the preparation of monodisperse thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) microcapsules in a microfluidic system. Based on the mechanism of shear force-driven break-off, aqueous droplets of monomer solution are continuously generated in an immiscible continuous phase containing photoinitiators. Under UV irradiation, activated initiators are diffused into the interface between the continuous phase and the aqueous droplets, which trigger polymerization of NIPAM monomers. The PNIPAM microcapsules produced are hollow microcapsules with a thin shell membrane, high monodispersity, and fast response to environmental temperature. In addition, the size of microcapsules produced can be manipulated by the flow rate of the continuous phase or aqueous phase and different concentrations of surfactant to control interfacial tension between continuous phase and aqueous phase. Furthermore, the versatility of this approach enables the preparation of monodisperse microcapsules having the capability to encapsulate various materials such as proteins and nanoparticles under mild conditions. The in situ microfluidic synthetic method provides a novel approach for the preparation of monodisperse hollow microcapsules via a one-pot route.     

Ring stain effect at room temperature in silver nanoparticles yields high electrical conductivity

We demonstrate that metallic rings formed spontaneously at room temperature via evaporation of aqueous drops containing silver nanoparticles (20-30 nm in diameter) exhibit high electrical conductivity (up to 15% of that for bulk silver). The mechanism underlying this self-assembly phenomena is the "ring stain effect", where self-pinning is combined with capillary flow to form a ring consisting of close-packed metallic nanoparticles along the perimeter of a drying droplet. Our macroscopic and microscopic (applying conductive atomic force microscopy) transport measurements show that the conductivity of the ring, which has a metallic brightness, is orders of magnitude larger than that of corresponding aggregates developed without the ring formation, where high conductivity is known to appear only after annealing at high temperature.     

Rapidly functionalized, water-dispersed carbon nanotubes at high concentration

Microwave-assisted functionalization of single-wall carbon nanotubes (SWNTs) in a mixture of nitric and sulfuric acids was carried out to synthesize highly water-dispersible nanotubes. Stable concentrations as high as 10 mg/mL were obtained in deionized water that are nearly 2 orders of magnitude higher than those previously reported. This was after only 3 min of functionalization reaction. Fourier transform infrared spectra showed the presence of carboxylated (-COOH) and acid sulfonated (-SO(2).OH or -SO(3)(-) H(+)) groups on the SWNTs. On the basis of elemental analysis, it was estimated that one out of three carbon atoms was carboxylated, while one out of 10 carbon atoms was sulfonated. The Raman spectra taken both in aqueous dispersion and in the solid phase indicated charge transfer from the SWNT backbone to the functional groups. Scanning electron microscope images of thin films deposited from an aqueous suspension showed that the SWNTs were aligned parallel to one another on the substrate. The images also indicated some reduction in average length of the nanotubes. Transmission electron microscope images of thin films from a dilute methanol dispersion showed that the SWNTs were extensively debundled. Laser light scattering particle size measurements did not show evidence for the existence of particles in the 3-800 nm size range, indicating that the functionalized SWNTs might have dispersed to have formed a true solution. Moreover, the microwave-processed SWNTs were found to contain significantly smaller amounts of the original iron catalyst relative to that present in the starting nanotubes. The electrical conductivity of a thermally annealed thin membrane obtained from the microwave-functionalized SWNTs was found to be the same as that of a similar membrane obtained from a suspension of the starting nanotubes.     

Polysilane spherulites and their high photoluminescence quantum yields

Large polysilane spherulites have been observed. The spherulites were prepared by controlling the removal rate of solvents from poly(n-butyl-n-pentylsilane) under a xylene atmosphere. The diameter of the spherulites was greater than 0.1 mm. The structure of the spherulites was compared with that of the polysilane powder by polarized microscopy, SEM, DSC, and x-ray diffractometry. A high photoluminescence quantum yield of 0.3 was obtained for the spherulites. © 1997 John Wiley & Sons, Inc.     

Variable high-pressure and concentration study of cyclohexane pyrolysis at high temperatures

A high-pressure and temperature cyclohexane pyrolysis shock tube study was completed with the goal of extending the experimental cyclohexane pyrolysis data to pressures relevant to current and future combustors and to investigate whether ring contraction products observed in high-pressure, supercritical phase cyclohexane and cycloalkane pyrolysis experiments can form at matching, and higher, pressures in the gas phase. The experiments in the current work were completed over a range of 950–1650 K and at nominal pressures of 40, 100, and 200 bar. No alkylcyclopentanes, possible ring contraction products, were observed to form under the conditions of the current study. The production of methylenecyclopentane and 1,3-cyclopentadiene, and the other three cyclic species quantified: cyclohexene, benzene, and toluene, increased significantly with a substantial increase in the initial fuel concentration. Two sets of experimental data obtained at 200 bar were compared with a literature and laboratory-generated model. Both models had difficulty capturing the propadiene and propyne profiles, and the literature model significantly overestimated the benzene observed in the set of experiments completed with the more dilute fuel mixture. The literature model was able to better predict propadiene, propyne, and benzene product profiles in the 200 bar set of experiments, which used a higher concentration of fuel in the test gas. These results suggest that despite both cyclohexane and benzene being well-studied and important species in combustion chemistry, their reaction pathways and reaction rates would benefit from further refinement.     

Reverse micelles template assisted fabrication of ZnO hollow nanospheres and hexagonal microtubes by a novel fast microemulsion-based hydrothermal method

ZnO hollow micro/nanostructures were fabricated by a novel fast hydrothermal method based on the microemulsion. The aqueous reverse micelles were used as templates and different amount of Zn²⁺ colloid was compelled to hydrolyze on its surface. Scanning electron microscopy indicates that the products grown in the solution with colloid volume concentration of 12.3 and 0.5 v.% are hollow nanospheres and hexagonal microtubes, respectively. It is believed that this difference should attribute to the initial shape of hydrolysate and the core/shell state of water/surfactant during hydrothermal treatment.     

Simultaneous fermentation and isomerization of xylose to ethanol at high xylose concentration

Applied Biochemistry and Biotechnology -     

Perturbation of phospholipid bilayer properties by ethanol at a high concentration

Atomistic molecular dynamics (MD) simulations have been carried out at 30 degrees C on a fully hydrated liquid crystalline lamellar phase of dimyrystoylphosphatidylcholine (DMPC) lipid bilayer with embedded ethanol molecules at 1:1 composition, as well as on the pure bilayer phase. The ethanol molecules are found to exhibit a preference to occupy regions near the upper part of the lipid acyl chains and the phosphocholine headgroups. The calculations revealed that the phosphocholine headgroup dipoles (P- --> N+) of the lipids prefer to orient more toward the aqueous layer in the presence of ethanol. It is noticed that the ethanol molecules modify the dynamic properties of both lipids as well as the water molecules in the hydration layer of the lipid headgroups. Both the in-plane "rattling" and out-of-plane "protrusion" motions of the lipids have been found to increase in the presence of ethanol. Most importantly, it is observed that the water molecules within the hydration layer of the lipid headgroups exhibit faster translational and rotational motions in the presence of ethanol. This arises due to faster dynamics of hydrogen bonds between lipid headgroups and water in the presence of ethanol.     

The aqueous catanionic system sodium perfluorooctanoate-dodecyltrimethylammonium bromide at low concentration

The interaction between sodium perfluorooctanoate (SPFO) and dodecyltrimethylammonium bromide (DTAB) was studied by several methods and it was found strongly synergistic. Above a mole fraction of SPFO in the surfactant mixture (alpha(SPFO))=0.38, the interaction is repulsive and increases with the content of SPFO in both, the overall mixture and micelles, whereas the interaction is attractive if DTAB is in excess. At alpha(SPFO)=0.38 the low miscibility between hydrocarbon and fluorocarbon is counterbalanced by the electrostatic attraction between the opposite charged head groups, and the micelle composition is ideal (i.e., the mole fraction of SPFO in micelles X(SPFO)=alpha(SPFO)=0.38). The solubility of fluorocarbon in hydrocarbon is lower than that of hydrocarbon in fluorocarbon. Micelles of DTAB act as a solvent for SPFO without important structural changes, whilst micelles of SPFO undergo important changes when dissolve DTAB. This asymmetry may be interpreted as caused by the difference in chain length that favors the inclusion of the shorter chain in micelles of the longer surfactant, but disfavors the opposite process. Above X(SPFO)=0.5 there is an excess adsorption of bromide ions on the mixed micelles surface, giving rise to a high zeta potential. Micelles of pure SPFO or pure DTAB show an important energy barrier which prevents micelle flocculation. The inclusion of SPFO in DTAB micelles produces a reduction of the energy barrier, which disappeared when alpha(SPFO)=0.5. This produces the flocculation of micelles giving rise to the formation of a non-birefringent coacervate, which is probably formed by unordered isometric clusters of micelles.     

The aqueous cationic system sodium undecenoate-dodecyltrimethylammonium bromide at low concentration

The aqueous sodium undecenoate (SUD) –dodecyltrimethylammonium bromide (DTAB) catanionic system was studied at low concentration. The system did not precipitate, even at a 1:1 SUD:DTAB proportion, but showed the formation of a coacervate in a range of surfactant mixture compositions. Micelles have a preferential composition of 0.37 mole fraction of SUD. This behavior is attributed to the presence of the double bond at the distal extreme of the SUD molecule, which can form hydrogen bonds with water. Consequently, the –CH=CH₂ group is situated at the interface between the hydrocarbon micelle core and water, reducing the interfacial free energy. Structural computations demonstrate that the mentioned SUD proportion produces complete coverage of the micelle surface by the double bonds.