Scaling up the production rate of nanofibers by needleless electrospinning from multiple ring

Mass production of nanofibers is crucial in both laboratory research and industry application of nanofibers. In this study, multiple ring spinnerets have been used to generate needleless electrospinning. Multiple polymer jets were produced from the top of each ring in the spinning process, resulting in thin and uniform nanofibers. Production rate of nanofibers increased gradually with the increase of the number of rings in the spinneret. Spinning performance of multiple ring electrospinning, namely the quality and production rate of the as-spun nanofibers, was dependent on experimental parameters like applied voltage and polymer concentration. Electric field analysis of multiple ring showed that high concentrated electric field was formed on the surface of each ring. Fiber diameter together with production rate of needleless electrospinning was dependent on the strength and distribution of the electric field of the spinneret. Needleless electrospinning from multiple ring can be further applied in both laboratory research and industry where large amount of nanofibers must be employed simultaneously. © 2014 The Korean Fiber Society and Springer Science+Business Media Dordrecht.

Chemistry, spectroscopy and analytical applications of certain chemiluminescent reactions

Chemiluminescence, the production of light from a chemical reaction, has found widespread use in analytical chemistry. Both tris (2, 2’-bipyridyl) ruthenium (II) and acidic potassium permanganate are chemiluminescence reagents that have been employed for the determination of a diverse range of analytes. This thesis encompasses some fundamental investigations into the chemistry and spectroscopy of these chemiluminescence reactions as well as extending the scope of their analytical applications. Specifically, a simple and robust capillary electrophoresis chemiluminescence detection system for the determination of codeine, O6-methylcodeine and thebaine is described, based upon the reaction of these analytes with chemically generated tris(2,2'-bipyridyl)ruthenium(III) prepared in sulfuric acid (0.05 M). The reagent solution was contained in a glass detection cell, which also held both the capillary and the cathode. The resultant chemiluminescence was monitored directly using a photomultiplier tube mounted flush against the base of the detection cell. The methodology, which incorporated a field amplification sample introduction procedure, realised detection limits (3a baseline noise) of 5 x 10~8 M for both codeine and O6-methylcodeine and 1 x 10~7 M for thebaine. The relative standard deviations of the migration times and the peak areas for the three analytes ranged from 2.2 % up to 2.5 % and 1.9 % up to 4.6 % respectively. Following minor instrumental modifications, morphine, oripavine and pseudomorphine were determined based upon their reaction with acidic potassium permanganate in the presence of sodium polyphosphate. To ensure no migration of the permanganate anion occurred, the anode was placed at the detector end whilst the electroosmotic flow was reversed by the addition of hexadimethrine bromide (0.001% m/v) to the electrolyte. The three analytes were separated counter to the electroosmotic flow via their interaction with a-cyclodextrin. The methodology realised detection limits (3 x S/N) of 2.5 x 10~7 M for both morphine and oripavine and 5 x 10~7 M for pseudomorphine. The relative standard deviations of the migration times and the peak heights for the three analytes ranged from 0.6 % up to 0.8 % and 1.5% up to 2.1 % respectively. Further improvements were made by incorporating a co-axial sheath flow detection cell. The methodology was validated by comparing the results realised using this technique with those obtained by high performance liquid chromatography (HPLC), for the determination of both morphine and oripavine in seven industrial process liquors. A complimentary capillary electrophoresis procedure with UV-absorption detection was also developed and applied to the determination of morphine, codeine, oripavine and thebaine in nine process liquors. The results were compared with those achieved using a standard HPLC method. Although over eighty papers have appeared in the literature on the analytical applications of acidic potassium permanganate chemiluminescence, little effort has been directed towards identifying the origin of the luminescence. It was found that chemiluminescence was generated during the manganese(III), manganese(IV) and manganese(VII) oxidations of sodium borohydride, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689 ± 5 nm and 734 ± 5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate or orthophosphoric acid environments respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K, exhibited two peaks with maxima at 688 nm and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution phase chemically induced phosphorescence of manganese(II). Thereby confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species. Additionally, these findings have had direct analytical application in that manganese(IV) was evaluated as a new reagent for chemiluminescence detection. The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 x S/N) for Mn(II), Fe(II), morphine and codeine of 5 x 10-8 M, 2.5 x 10-7 M, 7.5 x 10-8 M and 5 x 10-8M, respectively. The corrected emission spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm indicating that these chemiluminescence reactions also shared a common emitting species, excited manganese(II). Whilst several analytical problems were addressed in this thesis and answers to certain questions regarding the fundamentals of acidic potassium permanganate chemiluminescence were proposed, there are several areas that would benefit from further research. These are outlined in the final chapter of this thesis.

Multi-level virtual ring : a foundation network architecture to support peer-to-peer application in wireless sensor network

Two main problems prevent the deployment of peer-to-peer application in a wireless sensor network: the index table, which should be distributed stored rather than uses a central server as the director; the unique node identifier, which cannot use the global addresses. This paper presents a multi-level virtual ring (MVR) structure to solve these two problems.

The index table in MVR is distributed stored by using the DHT technique. MVR is constructed decentralized and runs on mobile nodes themselves, requiring no central server or interruption. Naming system in MVR uses natural names rather than global addresses to identify sensor nodes. The MVR can route directly on the name identifiers of the sensor nodes without being aware the location. Some sensor nodes are selected as the backbone nodes by the backbone selection algorithm and are placed on the different levels of the virtual rings. MVR hashes nodes’ identifiers on the virtual ring, and stores them at the backbone nodes. Furthermore, MVR adopts cross-level routing to improve the routing efficiency.

Experiments using ns2 simulator for up to 200 nodes show that the storage and bandwidth requirements of MVR grow slowly with the size of the network. Furthermore, MVR has demonstrated as self-administrating, fault-tolerant, and resilient under the different workloads.

Positron annihilation lifetime spectroscopy as a probe of free volume in plasticized solid polymer electrolytes

A recent report on the correlation between enhanced polymer mobility and ionic conductivity at room temperature in plasticized polyether-urethane solid polymer electrolytes (Forsyth et al.[1]), has prompted the present investigation. Positron annihilation lifetime spectroscopy (PALS) has been used to study the effect of plasticizer addition on the room temperature free volume characteristics of the crosslinked polyether-urethane. The addition of low molecular weight plasticizers to the polyether-urethane results in a constant or decreasing mean free volume cavity radius, as measured by the orthoPositronium lifetime τ₃, and a decreasing relative concentration of free volume cavities as measured by the ortho-Positronium intensity, I₃. It is postulated that the plasticizers interrupt polymer-polymer interactions by occupying the inter- and intra-chain free volume. The plasticizer structure influences the polymerplasticizer interactions which affect inter- and intra-chain separation and hence the free volume of the system. The decrease in polymer-polymer interaction and the increase in polymer-plasticizer interaction in turn influence the glass transition temperature behaviour.

Analysis of 5-hydroxyisoflavones by surface-enhanced Raman spectroscopy : genistein and methoxy derivatives

A series of 5-hydroxy-isoflavones—genistein, biochanin A, prunetin, and 4′,7-dimethoxygenistein—have been studied by surface-enhanced Raman spectroscopy (SERS). Citrate reduced silver colloids were employed as a standard technique to measure SER spectra over a range of pH and concentrations. Density functional theory calculations were used to assist in determining the mode of interaction of isoflavones with the silver nanoparticles. It is revealed that biochanin A and prunetin interact with the silver nanoparticles upon deprotonation of the 7- and the 4′-OH groups, respectively, to show SERS activity. Correlations of their spectra with SERS of genistein strongly support the presence of multiple interaction modes involving both of the OH groups in genistein, in a similar manner to daidzein. Surprisingly, however, under these conditions, the 5-OH group was found to be noninteractive as revealed by attempts to measure SERS of 4′,7-dimethoxygenistein. This was attributed partly to the low solubility and, more importantly, to the influence of steric hindrance, caused by the position of the pendant phenyl ring, which prevented interaction with the Ag colloid surface. These results complement recent work on daidzein and formononetin and provide further insight into understanding the SER spectra of isoflavones.

Surface-enhanced raman scattering spectroscopy of resveratrol

We report here, for the first time, the surface-enhanced Raman scattering (SERS) spectra of resveratrol using KNO₃-aggregated citrate-reduced silver (Ag) colloids. The technique provided a substantial spectral enhancement and therefore good quality spectra of resveratrol at parts per million (ppm) concentrations. The detection limit was found to be <1 μM, equivalent to <0.2 ppm. The SERS profile additionally closely resembled its normal solid-state Raman spectrum with some changes in relative intensity. These intensity changes, together with a precise band assignment aided by density functional theory calculations at the B3LYP/6–31G(d) level, allowed the determination of the structural orientation of the adsorbed resveratrol on the surface of the metal nanoparticles. In particular, the SERS spectra obtained at different resveratrol concentrations exhibited concentration-dependent features, suggesting an influence of surface coverage on the orientation of the adsorbed molecules. At a high concentration, an adoption of close-to-upright orientation of resveratrol adsorbed on the metal surface through the p-OH phenyl ring is favoured. The binding structure is, however, altered at lower surface coverage when the concentration decreases to a tilted orientation with the trans-olefin C=C bond aligning closer to parallel to the surface of the Ag nanoparticles.

Spectroscopic study of the effects of pressure media on high-pressure phase transitions in natrolite

Structural phase transitions in natrolite have been investigated as a function of pressure and different hydrostatic media using micro-Raman scattering and synchrotron infrared (IR) spectroscopy. Natrolite undergoes two reversible phase transitions at 0.86 and 1.53 GPa under pure water pressure medium. These phase transitions are characterized by the changes in the vibrational frequencies of four- and eight-membered rings related to the variations in the bridging T−O−T angles and the geometry of the elliptical eight-ring channels under pressure. Concomitant to the changes in the framework vibrational modes, the number of the O−H stretching vibrational modes of natrolite changes as a result of the rearrangements of the hydrogen bonds in the channels caused by a successive increase in the hydration level under hydrostatic pressure. Similar phase transitions were also observed at relatively higher pressures (1.13 and 1.59 GPa) under alcohol−water pressure medium. Furthermore, no phase transition was found up to 2.52 GPa if a lower volume ratio of the alcohol−water to natrolite was employed. This indicates that the water content in the pressure media plays a crucial role in triggering the pressure-induced phase transitions in natrolite. In addition, the average of the mode Grüneisen parameters is calculated to be about 0.6, while the thermodynamic Grüneisen parameter is found to be 1.33. This might be attributed to the contrast in the rigidity between the TO4 tetrahedral primary building units and other flexible secondary building units in the natrolite framework upon compression and subsequent water insertion.

Multi-level virtual ring : an architecture for content routing in wireless sensor network

Two main problems prevent the deployment of content delivery in a wireless sensor network: the address, which is widely used in the Internet as the identifier, is meaningless in wireless network, and the routing efficiency is a big concern in wireless sensor network. This paper presents an embedded multi-level ring (MVR) structure to address those two problems. The MVR uses names rather than addresses to identify sensor nodes. The MVR routes packets on the name identifiers without being aware the location. Some sensor nodes are selected as the backbone nodes and are placed on the different levels of the virtual rings. MVR hashes nodes and contents identifiers, and stores them at the backbone nodes. MVR takes the cross-level routing to improve the routing efficiency. Further, MVR is constructed decentralized and runs on the mobile nodes themselves, requiring no central control. Experiments using ns2 simulator for up to 200 nodes show that the storage and bandwidth requirements of MVR grow slowly with the size of the network. Furthermore, MVR has demonstrated as self-administrating, fault-tolerant, and resilient under the different workloads. We also discuss alternative implementation options, and future work.

Nature of crystalline particle assembly in ring shaped colloidal stains from concentrated dispersions

The drying of colloidal droplet suspensions is important in many realms of practical application and has sustained the interest of researchers over two decades. The arrangements of polystyrene and silica beads, both of diameter 1 μm, 10% by volume of solid deposited on normal glass (hydrophilic), and silicone (hydrophobic) surfaces evaporated from a suspension volume of 3 μL, were investigated. Doughnut shape depositions were found, imputing the influence of strong central circulation flows that resulted in three general regions. In the central region which had strong particle build-up, the top most layers of particle arrangement was confirmed to be disordered using power spectrum and radial distribution function analysis. On closer examination, this appeared more like frustrated attempts to crystallize into larger grains rather than beads arranging in a disordered fashion throughout the piling process. With an adapted micro-bulldozing operation to progressively remove layers of particles from the heap, we found that the later efforts to crystallize through lateral capillary inter-particle forces were liable to be undone once the particles contacted the disorganized particles underneath, which were formed out of the jamming of fast particles arriving at the surface. © 2014 Elsevier B.V.

Direct electrospinning of nanofibre yarns using a rotating ring collector

Nanofibres prepared by electrospinning typically have randomly oriented fibrous structure. They have large surface-to-volume (or weight) ratio and excellent porous characteristic, which have shown enormous potential in diverse applications. However, electrospun nanofibres are often prepared in the form of randomly orientated fibrous web, which are fragile and difficult to be tailored in fibrous structures. Herein, we demonstrate a novel yarn electrospinning method which uses a rotating ring collector to convert newly electrospun nanofibres directly into a continuous yarn. The use of ring collector separates the yarn formation from the electrospinning zone. The deposition of later-spun nanofibres to the inner surface of fibrous cone eliminates hooked or curled nanofibres in the final yarn. The effects of polymer concentration and operating parameters on nanofibre and yarn morphology, diameter and the ring collector on yarn twist feature were examined. The nanofibre yarns had a surface twist angle up to 54.4°, and tensile strength as high as 93.6 MPa (elongation at break 242.6%). Increasing twist levels improves tensile strength and strain values.

Rapid domino [3+2] cycloaddition, [4+2] cycloreversion, ring-opening and aromatisation of a fused oxanorbornane substrate

Heating a dioxa-bridged diene with a cyclobutane epoxide for 10 min under microwave conditions (150 °C) gave an unexpected aryloxanorbornane product (20%). This adduct is proposed to occur via a [3+2] dipolar cycloaddition, retro-Diels-Alder reaction, ring-opening and subsequent aromatisation.

Boron nitride nanosheets improve sensitivity and reusability of surface-enhanced raman spectroscopy

Surface enhanced Raman spectroscopy (SERS) is a useful multidisciplinary analytic technique. However, it is still a challenge to produce SERS substrates that are highly sensitive, reproducible, stable, reusable, and scalable. Herein, we demonstrate that atomically thin boron nitride (BN) nanosheets have many unique and desirable properties to help solve this challenge. The synergic effect of the atomic thickness, high flexibility, stronger surface adsorption capability, electrical insulation, impermeability, high thermal and chemical stability of BN nanosheets can increase the Raman sensitivity by up to two orders, and in the meantime attain long-term stability and extraordinary reusability not achievable by other materials. These advances will greatly facilitate the wider use of SERS in many fields.