Synthesis of caffeic acid and p-hydroxybenzoic acid molecularly imprinted polymers and their application for the selective extraction of polyphenols from olive mill waste waters

Using caffeic acid and p-hydroxybenzoic acid as templates, two molecularly imprinted polymers (MIPs) were prepared that were used for isolation of polyphenols from olive mill waste water samples (OMWWs) without previous pre-treatment. For the preparation of the caffeic acid MIPs 4-vinylpyridine, allylurea, allylaniline and methacrylic acid were tested as functional monomers, ethylene glycol dimethylacrylate (EDMA), pentaerythritol trimethylacrylate (PETRA) and divinylbenzene 80 (DVB80) as cross-linkers and tetrahydrofuran as porogen. For p-hydroxybenzoic acid 4-vinylpyridine, allylurea and allylaniline were tested as functional monomers, EDMA and PETRA as cross-linkers and acetonitrile as porogen. The performance of the synthesized polymers was evaluated against seven structurally related compounds by means of polymer-based HPLC. The two polymers that presented the most interesting properties were further evaluated by batch rebinding and from the derived isotherms their capacity and binding strength were determined. Using solid-phase extraction (SPE), their ability to recognize and bind the template molecule from an aqueous solution as well as the pH dependence of the binding strength were explored. After establishing the best SPE protocol, an aqueous model mixture of compounds and a raw OMWWs sample were loaded on the two best polymers. The result of the consecutive use of the two polymers on the same sample was explored. It was concluded that acidic conditions favour the recognition abilities of both polymers and that they can be used for a quick and efficient isolation of the polyphenol fraction directly from raw OMWW.

Clarification of rubber mill wastewater by a plant based biopolymer- comparison with common inorganic coagulants

Background: In this study, the efficiency of Guar gum as a biopolymer has been compared with two other widely used inorganic coagulants, ferric chloride (FeCl3) and aluminum chloride (AlCl3), for the treatment of effluent collected from the rubber-washing tanks of a rubber concentrate factory. Settling velocity distribution curves were plotted to demonstrate the flocculating effect of FeCl3, AlCl3 and Guar gum. FeCl3 and AlCl3 displayed better turbidity removal than Guar gum at all settling velocities.

Result: FeCl3, AlCl3 and Guar gum removed 92.8%, 88.2% and 88.1% turbidity, respectively, of raw wastewater at a settling velocity of 0.1 cm min-1, respectively. Scanning electron microscopic (SEM) study conducted on the flocs revealed that Guar gum and FeCl3produced strong intercoiled honeycomb patterned floc structure capable of entrapping suspended particulate matter. Statistical experimental design Response Surface Methodology (RSM) was used to design all experiments, where the type and dosage of flocculant, pH and mixing speed were taken as control factors and, an optimum operational setting was proposed.

Conclusion: Due to biodegradability issues, the use of Guar gum as a flocculating agent for wastewater treatment in industry is highly recommended.

A comparative study of biopolymers and alum in the separation and recovery of pulp fibres from paper mill effluent by flocculation

Recovery of cellulose fibres from paper mill effluent has been studied using common polysaccharides or biopolymers such as Guar gum, Xanthan gum and Locust bean gum as flocculent. Guar gum is commonly used in sizing paper and routinely used in paper making. The results have been compared with the performance of alum, which is a common coagulant and a key ingredient of the paper industry. Guar gum recovered about 3.86 mg/L of fibre and was most effective among the biopolymers. Settling velocity distribution curves demonstrated that Guar gum was able to settle the fibres faster than the other biopolymers; however, alum displayed the highest particle removal rate than all the biopolymers at any of the settling velocities. Alum, Guar gum, Xanthan gum and Locust bean gum removed 97.46%, 94.68%, 92.39% and 92.46% turbidity of raw effluent at a settling velocity of 0.5 cm/min, respectively. The conditions for obtaining the lowest sludge volume index such as pH, dose and mixing speed were optimised for guar gum which was the most effective among the biopolymers. Response surface methodology was used to design all experiments, and an optimum operational setting was proposed. The test results indicate similar performance of alum and Guar gum in terms of floc settling velocities and sludge volume index. Since Guar gum is a plant derived natural substance, it is environmentally benign and offers a green treatment option to the paper mills for pulp recycling.

Non-Markovian qubit dynamics in a circuit-QED setup

We consider a circuit-QED setup that allows the induction and control of non-Markovian dynamics of a qubit. Non-Markovianity is enforced over the qubit by means of its direct coupling to a bosonic mode which is controllably coupled to another qubit-mode system. We show that this configuration can be achieved in a circuit-QED setup consisting of two initially independent superconducting circuits, each formed by one charge qubit and one transmission-line resonator, which are put in interaction by coupling the resonators to a current-biased Josephson junction. We solve this problem exactly and then proceed with a thorough investigation of the emergent non-Markovianity in the dynamics of the qubits. Our study might serve the context for the first experimental assessment of non-Markovianity in a multielement solid-state device.

Nucleoside Azide-Alkyne Cycloaddition Reactions Under Solvothermal Conditions or Using Copper Vials in a Ball Mill

Novel nucleoside analogues containing photoswitchable moieties were prepared using 'click' cycloaddition reactions between 5 '-azido-5 '-deoxythymidine and mono- or bis-N-propargylamide-substituted azobenzenes. In solution, high to quantitative yields were achieved using 5mol% Cu(I) in the presence of a stabilizing ligand. 'Click' reactions using the monopropargylamides were also effected in the absence of added cuprous salts by the application of liquid assisted grinding (LAG) in metallic copper reaction vials. Specifically, high speed vibration ball milling (HSVBM) using a 3/32('') (2.38mm) diameter copper ball (62mg) at 60Hz overnight in the presence of ethyl acetate lead to complete consumption of the 5 '-azido nucleoside with clean conversion to the corresponding 1,3-triazole.

Numerical analysis of impact events in a centrifugal impact pin mill

Milling is an important operation in many industries, such as mining and pharmaceutical. Although the comminution process during milling has been extensively studied, the material fragmentation mechanisms in a mill are still not well understood partly because of the lack of an understanding on the local stressing and dynamic information under operational conditions in mills. This paper presents a DEM simulation of particle dynamics and impact events in a centrifugal impact pin mill. The main focus is the statistical characteristics of the dominant stressing modes during the milling process. The frequency, velocity and force of the different impact events between particles and mill components, or between particles, are analysed. © 2013 AIP Publishing LLC.

2P/Encke, the Taurid complex NEOs and the Maribo and Sutter's Mill meteorites

Aims. 2P/Encke is a short period comet that was discovered in 1786 and has been extensively observed and studied for more than 200years. The Taurid meteoroid stream has long been linked with 2P/Encke owing to a good match of their orbital elements, even thoughthe comet’s activity is not strong enough to explain the number of observed meteors. Various small near-Earth objects (NEOs) havebeen discovered with orbits that can be linked to 2P/Encke and the Taurid meteoroid stream. Maribo and Sutter’s Mill are CM typecarbonaceous chondrite that fell in Denmark on January 17, 2009 and April 22, 2012, respectively. Their pre-atmospheric orbits placethem in the middle of the Taurid meteoroid stream, which raises the intriguing possibility that comet 2P/Encke could be the parentbody of CM chondrites.
Methods. To investigate whether a relationship between comet 2P/Encke, the Taurid complex associated NEOs, and CM chondritesexists, we performed photometric and spectroscopic studies of these objects in the visible wavelength range. We observed 2P/Enckeand 10 NEOs on August 2, 2011 with the FORS instrument at the 8.2 m Very Large Telescope on Cerro Paranal (Chile).
Results. Images in the R filter, used to investigate the possible presence of cometary activity around the nucleus of 2P/Encke andthe NEOs, show that no resolved coma is present. None of the FORS spectra show the 700 nm absorption feature due to hydratedminerals that is seen in the CM chondrite meteorites. All objects show featureless spectra with moderate reddening slopes at λ < 800nm. Apart for 2003 QC10 and 1999 VT25, which show a flatter spectrum, the spectral slope of the observed NEOs is compatible withthat of 2P/Encke. However, most of the NEOs show evidence of a silicate absorption in lower S/N data at λ > 800 nm, which is notseen in 2P/Encke, which suggests that they are not related.
Conclusions. Despite similar orbits, we find no spectroscopic evidence for a link between 2P/Encke, the Taurid complex NEOs andthe Maribo and Sutter’s Mill meteorites. However, we cannot rule out a connection to the meteorites either, as the spectral differencesmay be caused by secondary alteration of the surfaces of the NEOs. 

A Computational Approach for Simulating P-type Silicon Piezoresistor Using Four Point Bending Setup

The piezoresistance effect is defined as change in resistance due to applied stress. Silicon has a relatively large piezoresistance effect which has been known since 1954. A four point bending setup is proposed and designed to analyze the piezoresistance effect in p-type silicon. This setup is used to apply uniform and uniaxial stress along the <110> crystal direction. The main aim of this work is to investigate the piezoresistive characteristic of p-type resistors as a function of doping concentrations using COMSOL Multiphysics. Simulation results are compared with experimental data.

Synthesis of novel pyrophosphorothiolate-linked dinucleoside cap analogues in a ball mill

Michaelis–Arbuzov reactions of S-aryl disulfide derivatives of 3′-thiothymidine or 5′-thioadenosine with tris(trimethylsilyl) phosphite proceeded in high yields to the corresponding phosphorothiolate monoesters. Subsequent hydrolytic desilylation and phosphate coupling were effected in one-pot using liquid-assisted grinding in a vibration ball mill. Novel 3′,5′- and 5′,5′-pyrophosphorothiolate-linked dinucleoside cap analogues were thereby prepared.

Environmental impact assessment: looking at sediments in Nootka Sound for traces of pulp mill effluent

Senior thesis written for Oceanography 445

Development of CBCT-based prostate setup correction strategies and impact of rectal distension.

BACKGROUND: Cone-beam computed tomography (CBCT) image-guided radiotherapy (IGRT) systems are widely used tools to verify and correct the target position before each fraction, allowing to maximize treatment accuracy and precision. In this study, we evaluate automatic three-dimensional intensity-based rigid registration (RR) methods for prostate setup correction using CBCT scans and study the impact of rectal distension on registration quality. METHODS: We retrospectively analyzed 115 CBCT scans of 10 prostate patients. CT-to-CBCT registration was performed using (a) global RR, (b) bony RR, or (c) bony RR refined by a local prostate RR using the CT clinical target volume (CTV) expanded with 1-to-20-mm varying margins. After propagation of the manual CT contours, automatic CBCT contours were generated. For evaluation, a radiation oncologist manually delineated the CTV on the CBCT scans. The propagated and manual CBCT contours were compared using the Dice similarity and a measure based on the bidirectional local distance (BLD). We also conducted a blind visual assessment of the quality of the propagated segmentations. Moreover, we automatically quantified rectal distension between the CT and CBCT scans without using the manual CBCT contours and we investigated its correlation with the registration failures. To improve the registration quality, the air in the rectum was replaced with soft tissue using a filter. The results with and without filtering were compared. RESULTS: The statistical analysis of the Dice coefficients and the BLD values resulted in highly significant differences (p<10(-6)) for the 5-mm and 8-mm local RRs vs the global, bony and 1-mm local RRs. The 8-mm local RR provided the best compromise between accuracy and robustness (Dice median of 0.814 and 97% of success with filtering the air in the rectum). We observed that all failures were due to high rectal distension. Moreover, the visual assessment confirmed the superiority of the 8-mm local RR over the bony RR. CONCLUSION: The most successful CT-to-CBCT RR method proved to be the 8-mm local RR. We have shown the correlation between its registration failures and rectal distension. Furthermore, we have provided a simple (easily applicable in routine) and automatic method to quantify rectal distension and to predict registration failure using only the manual CT contours.