Ultrasonic enhancement of the supercritical extraction from ginger

This work examines the concurrent use of power ultrasound during the extraction of pungent compounds from a typical herb (ginger) with supercritical CO₂. A power ultrasonic transducer with an operating frequency of 20 kHz is connected to an extraction vessel and the extraction of gingerols from freeze-dried ginger particles (4–8 mm) is monitored. In the presence of ultrasound, we find that both the extraction rate and the yield increase. The higher extraction rate is attributed to disruption of the cell structures and an increase in the accessibility of the solvent to the internal particle structure, which enhances the intra-particle diffusivity. While cavitation would readily account for such enhancement in ambient processes, the absence of phase boundaries should exclude such phenomena above the critical point. Possible alternate mechanisms for the cell structure damage are discussed.     

Polyimide polydimethylsiloxane triblock copolymers for thin film composite gas separation membranes

This article demonstrates the successful fabrication of thin‐film‐composite (TFC) membranes containing well‐defined soft‐hard‐soft triblock copolymers. Based on “hard” polyimide (PI) and “soft” polydimethylsiloxane (PDMS), these triblock copolymers (PDMS‐b‐PI‐b‐PDMS), were prepared via condensation polymerization, and end‐group allylic functionalization to prepare the polyimide component and subsequent “click” coupling with the soft azido functionalized PDMS component. The selective layer consisted of pure PDMS‐b‐PI‐b‐PDMS copolymers which were cast onto a precast crosslinked‐PDMS gutter layer which in turn was cast onto a porous polyacrylonitrile coated substrate. The TFC membranes' gas transport properties, primarily for the separation of carbon dioxide (CO₂) from nitrogen (N₂), were determined at 35 °C and at a feed pressure of 2 atm. The TFC membranes showed improvements in gas permselectivity with increasing PDMS weight fraction. These results demonstrate the ability for glassy, hard polymer components to be coated onto otherwise incompatible surfaces of highly permeable soft TFC substrates through covalent coupling. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3372–3382     

Hydrocarbon solubility,permeability, and competitive sorption effects in polymer of intrinsic microporosity (PIM‐1) membranes

The sorption and permeation of pentane, hexane, and toluene through highly permeable polymer of intrinsic microporosity (PIM‐1) membranes were investigated. It was established that the hydrocarbons sorbed strongly within the micro‐void regions of the PIM‐1 membrane. The sorption concentration was similar for the paraffins, pentane and hexane, but greater for aromatic toluene at high vapor activities. The magnitude of the hydrocarbon permeability was associated with the critical temperature of the hydrocarbon. The PIM‐1 membrane displayed selectivity for the three hydrocarbons over CO₂. As a consequence, the presence of the three hydrocarbons dramatically reduced the permeability of CO₂ and N₂ under mixed gas–vapor conditions to 68%–95% below the dry gas value. For all three hydrocarbons the N₂ permeability was more strongly impacted than CO₂ permeability, and hence the ideal CO₂/N₂ selectivity of PIM‐1 increased. It was determined that CO₂ and N₂ solubility decreased because of hydrocarbon competitive sorption while CO₂ and N₂ diffusivity also decreased because of anti‐plasticization, which was due to the presence of hydrocarbon clusters within the membrane structure. There was a clear correlation between the magnitude of anti‐plasticization and the critical temperature of the hydrocarbon. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 397–404     

High‐performance thin film composite membranes with well‐defined poly(dimethylsiloxane)‐b‐poly(ethylene glycol) copolymer additives for CO2 separation

A series of well‐defined diblock copolymers (BCPs) consisting of poly(ethylene glycol) (PEG) and poly(dimethylsiloxane) (PDMS) were synthesized and blended with commercially available PEBAX® 2533 to form the active layer of thin‐film composite (TFC) membranes, via spin‐coating. BCPs with a PEG component ranging from 1 to 10 kDa and a PDMS component ranging from 1 to 10 kDa were synthesized by a facile condensation reaction of hydroxyl terminated PEG and carboxylic acid functionalized PDMS. The BCP/PEBAX® 2533 blends up to 50 wt % on cross‐linked PDMS gutter layers were tested at 35 °C and 350 kPa. TFC membranes containing BCPs of 1 kDa PEG and 1–5 kDa PDMS produced optimal results with CO₂ permeances of approximately 1000 GPU which is an increase up to 250% of the permeance of pure PEBAX® 2533 composite membranes, while maintaining a CO₂/N₂ selectivity of 21. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1500–1511     

Determination of the size distribution of sonoluminescence bubbles in a pulsed acoustic field

A simple method is described for determining the size of sonoluminescence bubbles generated by acoustic cavitation. The change in the intensity of sonoluminescence, from 4 ms pulses of 515 kHz ultrasound, as a function of the "off" time between acoustic pulses, is the basis of the method. The bubble size determined in water was in the range of 2.8-3.7 mum.     

Sonochemical synthesis of liquid-encapsulated lysozyme microspheres

Liquid-encapsulated lysozyme microspheres were successfully synthesized using a sonochemical method. The encapsulation of four different liquids, namely, sunflower oil, tetradecane, dodecane and perfluorohexane on the formation, stability and morphology of the lysozyme microspheres was studied. Among the four different liquids used for encapsulation, perfluorohexane-filled microspheres were found to be most stable in the dried state with a narrow size distribution. In order to explore the possibility of encapsulating biofunctional molecules (e.g., drugs) within these microspheres, liquids containing a fluorescent dye (Nile red) were encapsulated and the ultrasound-induced release of these dye-loaded liquids was studied. The fluorescence data for the liquid-filled lysozyme microspheres demonstrated the potential use of the sonochemical technique for synthesizing these “vehicles” for the encapsulation and the controlled delivery of dyes, flavours, fragrances or drugs.     

Sonoluminescence and sonochemiluminescence from a microreactor

Micromachined pits on a substrate can be used to nucleate and stabilize microbubbles in a liquid exposed to an ultrasonic field. Under suitable conditions, the collapse of these bubbles can result in light emission (sonoluminescence, SL). Hydroxyl radicals (OH()) generated during bubble collapse can react with luminol to produce light (sonochemiluminescence, SCL). SL and SCL intensities were recorded for several regimes related to the pressure amplitude (low and high acoustic power levels) at a given ultrasonic frequency (200kHz) for pure water, and aqueous luminol and propanol solutions. Various arrangements of pits were studied, with the number of pits ranging from no pits (comparable to a classic ultrasound reactor), to three-pits. Where there was more than one pit present, in the high pressure regime the ejected microbubbles combined into linear (two-pits) or triangular (three-pits) bubble clouds (streamers). In all situations where a pit was present on the substrate, the SL was intensified and increased with the number of pits at both low and high power levels. For imaging SL emitting regions, Argon (Ar) saturated water was used under similar conditions. SL emission from aqueous propanol solution (50mM) provided evidence of transient bubble cavitation. Solutions containing 0.1mM luminol were also used to demonstrate the radical production by attaining the SCL emission regions.     

CHARACTERIZATION OF NANOSTRUCTURES:TOOLS AND CHALLENGES

Apart from long-known and applied nanostructures like carbon black for tyres or pigments for coatings nanotechnology has created highly sophisticated structures used for nano/molecular electronics,diagnostics,drug delivery, UV-absorbers etc.Often the main question to be solved analytically is the local determination of tiny amounts of chemicals resulting in an ever increasing need for highly sensitive as well as locally resolved techniques.Applications of techniques like mass spectroscopy,transmission el...     

Dynamics of counterion binding during acoustic nebulisation of surfactant solutions

A metal ion (Cu(2+)) and a complex copper species, copper (II) bis-bipyridine, were used as alternate counterions in an aqueous surfactant solution of sodium dodecylbenzenesulfonate (SDBS) to investigate the dynamics of counterion interactions in an acoustic field. Sonoluminescence spectral studies showed that such counterions were able to replace sodium ions at the interface, even when the interface was rapidly oscillating under the acoustic field. Ultrasound induced nebulisation was then used to probe the interfacial profile of surfactant and bound counterions in a dynamic environment. At low bulk concentrations, the copper (II) bis-bipyridine cation was more effective at enhancing the loading of the dodecylbenzenesulfonate anion on the interface, due to its documented greater binding ability. However, at higher bulk concentrations, the movement of this cation is limited by its larger size and the smaller Cu(2+) cation is more effective in enhancing the loading of the dodecylbenzenesulfonate anion. The results show that under dynamic conditions, the surface concentrations are governed by mass transfer kinetics rather than equilibrium thermodynamics.     

Photochromic and fluorescence properties of coumarin fulgimides

Four new fulgimides possessing a fluorescent coumarin unit were synthesized from the corresponding fulgides, and their photochromic as well as fluorescence properties were investigated. The open-ring forms of coumarin fulgimides were found to exhibit fluorescence in the visible region. Upon exposure to UV light, the fulgimides were transformed into the nonfluorescent closed-ring forms, which can be reverted to the initial fluorescent open-ring forms on exposure to visible light. The efficiency of quenching of fluorescence was as high as 95% at the photostationary state of UV irradiation.