Nanofiltration membranes modified with aromatic polyamide dendrimers active layers

This thesis describes the modification of the commercial TFC-S nanofiltration membrane with shape-persistent dendritic architectures. Amphiphilic aromatic polyamide dendrimers (G1-G3) are synthesized via a divergent approach and used for membrane modification by direct percolation. The permeate samples collected from the percolation experiments are analyzed by UV-Vis spectroscopy to instantly monitor the influence of dendrimer generations on percolation behaviors and new active layer formation. The membrane structures are further characterized by Rutherford backscattering spectrometry (RBS) and atomic force microscopy (AFM) techniques, suggesting a low-level accumulation of dendrimers inside the TFC-S NF membranes and subsequent formation of an additional aramide dendrimer active layer. Thus, all the modified TFC-S membranes have a double active layer structure. A PES-PVA film is used as a control membrane showing that structural compatibility between the dendrimer and supports plays an important role in the membrane modification process. The performance of modified TFC-S membrane is evaluated on the basis of rejection abilities of a variety of water contaminants having a range of sizes and chemistry. As the water flux is inversely proportional to the thickness of the active layer, we optimize the amount of dendrimers deposited for specific contaminants to improve the solute rejection while maintaining high water flux.

Synthesis and characterization of fluorescent poly(aromatic amide) dendrimers

The synthesis of a series of poly(aromatic amide) dendrimers up to the second generation is described herein. The AB, building block used throughout the synthesis of the dendrimers was the allyl ester of 3,5-diaminocinnamic acid, which has been synthesized from 3,5-dinitrobenzoic acid in good yield with use of a four-step procedure. Dendron synthesis was achieved via a convergent approach with use of a sequence of deprotection/coupling steps. Two commercially available alcohols, L-menthol and citronellol, were coupled to the AB(2) monomer by using an alkyl diacid spacer and two core units; 1,7-diaminoheptane and tris(2-aminoethyl)amine have been used to produce the final dendrimers. Characterization was carried out by NMR and IR spectroscopies, MALDI-TOF mass spectrometry, GPC, and DSC. The novel monomer and dendritic derivatives exhibited a strong fluorescence emission in the visible region (lambda approximate to 500 nm) of the spectrum and a weak emission in the near-infrared (lambda approximate to 850 nm) upon excitation in the near-UV region. The fluorescence emission characteristics were found to be solvent and dendrimer generation dependent.

Suodatuskalvojen toimivuuden arviointi paperiteollisuuden sovelluksissa

Työn tavoitteena oli etsiä vaihtoehtoja paperiteollisuuden kiertovesien ja pastapitoisten jätevesien suodatusprosesseissa tällä hetkellä käytössä oleville kalvoille. Työssä pyrittiin myös määrittämään tekijöitä, joiden avulla voitaisiin ennustaa polymeerikalvon käyttäytymistä erilaisissa paperiteollisuuden kalvosovelluksissa. Työn kirjallisessa osassa tarkasteltiin polymeerikalvojen ominaisuuksia, jotka vaikuttavat kalvojen käyttäytymiseen suodatusprosesseissa. Työssä esiteltiin myös tavallisimmat kalvomateriaalit ja polymeerikalvojen valmistustavat sekä paperiteollisuuden kalvosovelluksia. Paperiteollisuuden kalvosuodatussovellukset eroavat toisistaan huomattavasti toimintaolosuhteiltaan ja käyttötarkoituksiltaan. Tästä johtuen on hankalaa löytää yhteisiä tekijöitä, joiden perusteella voitaisiin ennustaa kalvon käyttäytymistä eri sovelluksissa. Kalvon hydrofiilisyyden todettiin kuitenkin vaikuttavan positiivisesti suodatustapahtumaan useissa sovelluksissa. Kokeellisessa osassa verrattiin erilaisten polymeerikalvojen ja referenssikalvojen toimintaa happaman kirkkaan suodoksen ja pastapitoisen veden suodatuksessa. Kirkkaan suodoksen suodatuskokeet tehtiin UPM-Kymmene Oy:n Kaukaan tehtailla. Pastapitoista jätevettä mallinnettiin syöttöpanoksilla, jotka tehtiin laimentamalla CTC:n valmistamaa LWC-pastaa. Suodatukset tehtiin CR 200/1- ja CR 550/10 -suodattimilla. Kirkkaan suodoksen suodatuksissa käytettiin referenssikalvona regeneroidusta selluloosasta ja pastapitoisen veden suodatuksessa aromaattisesta polyamidista valmistettua kalvoa. Kirkkaan suodoksen koesuodatusten perusteella todettiin, ettei minkään vertailtavan ultrasuodatuskalvon suodatuskapasiteetti ollut yhtä korkea kuin referenssikalvon. Referenssikalvon toiminta suodatuksessa oli myös vakaata syötön laadun muutoksista huolimatta. Todennäköisesti referenssikalvon erittäin hydrofiilinen luonne tekee siitä vertailtavia kalvoja sopivamman kirkkaan suodoksen suodatukseen. Pastapitoisen veden suodatustulosten perusteella referenssikalvolle löytyi useita potentiaalisia korvaajia. Näistä parhaan kalvon valitseminen edellyttää kuitenkin jatkotutkimuksia. SEM-analyysituloksista huomattiin, että tietyntyyppinen kalvorakenne parantaa kalvon toimintaa pastapitoisen veden suodatuksessa.

Oxidation studies of a novel barrier polymer system

The thermal oxidation of two model compounds representing the aromatic polyamide, MXD6 (poly m-xylylene adipamide) have been investigated. The model compounds (having different chemical structures, viz, one corresponding to the aromatic part of the chain and the other to the aliphatic part), based on the structure of MXD6 were prepared and reactions with different concentrations of cobalt ions examined with the aim of identifying the role of the different structural components of MXD6 on the mechanism of oxidation. The study showed that cobalt, in the presence of sodium phosphite (which acts as an antioxidant for MXD6 and the model compounds), increases the oxidation of the model compounds. It is believed that the cobalt acts predominantly as a catalyst for the decomposition of hydroperoxides, formed during oxidation of the models in the melt phase, to free radical products and to a lesser extent as a catalyst for the initiation of the oxidation reaction by complex formation with the amide, which is more likely to take place in the solid phase. An oxidation cycle has been proposed consisting of two parts both of which will occur, to some extent under all conditions of oxidation (in the melt and in the solid phase), but their individual predominance must be determined by the prevailing oxygen pressure at the reaction site. The different aspects of this proposed mechanism were examined from extensive model compound studies, and the evidence based on the nature of product formation and the kinetics of these reactions. Main techniques used to compare the rates of oxidation and the study of kinetics included, oxygen absorption, FT-IR, UV and TGA. HPLC was used for product separation and identification.

Application of Nanofiltration to the Treatment of Acid mine Drainage Waters

This study investigated the separation of uranium and other elements in high concentrations from acid mine waters at Caldas Uranium Mining, in the southeast of Brazil, using nanofiltration membranes. Nanofiltrarion is widely used in water treatment due to the lower energy requirements and higher yields than reverse osmosis. Separation characteristics are dependent on both the molecular size and charge of the dissolved species in the feed solution as well as membrane properties. In this investigation the potential of nanofiltration to removed dissolved species like uranium from acid mine water drainage was measured. Two composite aromatic polyamide commercially membranes of FilmTec/Dow were tested and it found that uranium rejections of greater than 90% and also showed potential for the separation of aluminum and manganese.

Design of advanced reverse osmosis and nanofiltration membranes for water purification

Most commercially available reverse osmosis (RO) and nanofiltration (NF) membranes are based on the thin film composite (TFC) aromatic polyamide membranes. However, they have several disadvantages including low resistance to fouling, low chemical and thermal stabilities and limited chlorine tolerance. To address these problems, advanced RO/NF membranes are being developed from polyimides for water and wastewater treatments. The following three projects have resulted from my research. (1) Positively charged and solvent resistant NF membranes. The use of solvent resistant membranes to facilitate small molecule separations has been a long standing industry goal of the chemical and pharmaceutical industries. We developed a solvent resistant membrane by chemically cross-linking of polyimide membrane using polyethylenimine. This membrane showed excellent stability in almost all organic solvents. In addition, this membrane was positively charged due to the amine groups remaining on the surface. As a result, high efficiency (> 95%) and selectivity for multivalent heavy metal removal was achieved. (2) Fouling resistant NF membranes. Antifouling membranes are highly desired for “all” applications because fouling will lead to higher energy demand, increase of cleaning and corresponding down time and reduced life-time of the membrane elements. For fouling prevention, we designed a new membrane system using a coating technique to modify membrane surface properties to avoid adsorption of foulants like humic acid. A layer of water-soluble polymer such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl sulfate (PVS) or sulfonated poly(ether ether ketone) (SPEEK), was adsorbed onto the surface of a positively charged membrane. The resultant membranes have a smooth and almost neutrally charged surface which showed better fouling resistance than both the positively charged NF membranes and commercially available negatively charged NTR-7450 membrane. In addition, these membranes showed high efficiency for removal of multivalent ions (> 95% for both cations and anions). Therefore, these antifouling surfaces can be potentially used for water softening, water desalination and wastewater treatment in a membrane bioreactor (MBR) process. (3) Thermally stable RO membranes. Commercial RO membranes cannot be used at temperature higher than 45°C due to the use of polysulfone substrate, which often limits their applications in industries. We successfully developed polyimides as the membrane substrate for thermally stable RO membranes due to their high thermal resistance. The polyimide-based composite polyamide membranes showed desalination performance comparable to the commercial TFC membrane. However, the key advantage of the polyimide-based membrane is its high thermal stability. As the feed temperature increased from 25oC to 95oC, the water flux increased 5 - 6 times while the salt rejection almost kept constant. This membrane appears to provide a unique solution for hot water desalination and also a feasible way to improve the water productivity by increasing the operating temperature without any drop in salt rejection.

Chiral poly(aromatic amide ester) dendrimers bearing an amino acid derived C-3-symmetric core: synthesis and properties

The effect of hyperbranched macromolecular architectures (dendrimers) upon chirality has received significant attention in recent years in the light of the proposal of amplification of chirality. In particular, several studies have been carried out on the chiroptical properties of dendrimers that contain a chiral core and achiral branches in order to determine if the chirality of the central core can be transmitted to the distal. region of the macromolecule. In addition to interest of a pure academic nature, the presence of such chiral conformational order would be extremely useful in the development of asymmetric catalysts. In this paper, a novel class of chiral dendrimers is described - these perfect hyperbranched macromolecules have been prepared by a convergent route by the coupling of a chiral central core based upon tris(2-aminoethyl)amine and poly(aromatic amide ester) dendritic branches. The chiral properties of these dendrimers have been investigated by detailed optical rotation studies and circular dichroism analysis; the results of these studies are described herein. (C) Wiley-VCH Verlag GmbH Co.

Distamycin-NA: A DNA Analog with an Aromatic Heterocyclic Polyamide Backbone. Part 1. Synthesis and structural analysis of monomers and dimers containing the nucleobase uracil

The synthesis of the monomeric building block 13 and its constitutional isomer 12 of a new type of DNA analog, distamycin-NA, is presented (Schemes 1 and 2). This building block consists of a uracil base attached to a thiophene core unit via a biaryl-like axis. Next to the biaryl-like axis on the thiophene chromophore, a carboxy and an amino substituent are located allowing for oligomerization via peptide coupling. The proof of constitution and the conformational preferences about the biaryl-like axis were established by means of X-ray analyses of the corresponding nitro derivatives 10 and 11. Thus, the uracil bases are propeller-twisted relative to the thiophene core, and bidentate H-bonds occur between two uracil bases in the crystals. The two amino-acid building blocks 12 and 13 were coupled to give the dimers 15 and 16 using dicyclohexylcarbodiimide (DCC) in THF/LiCl and DMF, respectively. While the dimer 15 showed no atropisomerism on the NMR time scale at room temperature, its isomer 16 occurred as distinct diastereoisomers due to the hindered rotation around its biaryl-like axis. Variable-temperature 1H-NMR experiments allowed to determine a rotational barrier of 19 ± 1 kcal/mol in 16. The experimental data were complemented by AM1 calculations.

Distamycin-NA: A DNA analog with an aromatic heterocyclic polyamide backbone. Part 2. Solid-phase synthesis of distamycin-NAs containing the nucleobase uracil: Unexpected solvent participation in the coupling step

10.1002/hlca.19980810512.abs The synthesis of the Fmoc-protected amino acid 2 is presented. First attempts of amide-bond formation to the homodimer 4 in solution showed only poor coupling yields indicative for the low reactivity of the amino and carboxy groups in the building blocks 1 and 2, respectively (Scheme 1). Best coupling yields were found using dicyclohexylcarbodiimide (DCC) without any additive. The oligomerization of building block 2 adopting the Fmoc ((9H-fluoren-9-ylmethoxy)carbonyl) solid-phase synthesis yielded a mixture of N-terminal-modified distamycin-NA derivatives. By combined HPLC and MALDI-TOF-MS analysis, the N-terminal functional groups could be identified as acetamide and N,N-dimethylformamidine functions, arising from coupling of the N-terminus of the growing chain with residual AcOH or DCC-activated solvent DMF. An improved preparation of building block 2 and coupling protocol led to the prevention of the N-terminal acetylation. However, ‘amidination’ could not be circumvented. A thus isolated tetramer of 2, containing a lysine unit at the C-terminus and a N,N-dimethylformamidine-modified N-terminus, not unexpectedly, showed no complementary base pairing to DNA and RNA, as determined by standard UV-melting-curve analysis.

First Example of Organocatalysis by Polystyrene-Supported PAMAM Dendrimers: Highly Efficient and Reusable Catalyst for Knoevenagel Condensations

This paper describes the first use of polystyrene-supported poly(amidoamine) (PAMAM) dendrimers as heterogeneous basic organocatalysts for carbon–carbon bond formation. Polystyrene-supported PAMAM dendrimers of first, second and third generations have been used as reusable base catalysts in Knoevenagel condensations of carbonyl compounds with active methylene compounds. The reactions proceed in short periods of time and with 100% selectivity. This novel catalyst eliminates the use of aromatic and halogenated solvents, as well as complex purification processes. The catalysts can be recycled ten times.

Catalysis by Polymer Supported Dendrimers, their Metal Complexes and Nanoparticle Conjugates

The present thesis has described the development of some heterogeneous catalysts based on polymer supported dendrimers. Attachment of dendrimers to crosslinked polymer produced new catalysts with combined benefits of both dendrimers and heterogeneous catalysts. These were used as heterogeneous catalysts in selected reactions. All possible attempts were taken to avoid halogenated and aromatic solvents and toxic reagents. In short the present work has dealt with development of environmental friendly catalysts based on dendrimers.

Molecular Variations In Aromatic Cosolutes: Critical Role In The Rheology Of Cationic Wormlike Micelles.

Wormlike micelles formed by the addition to cetyltrimethylammonium bromide (CTAB) of a range of aromatic cosolutes with small molecular variations in their structure were systematically studied. Phenol and derivatives of benzoate and cinnamate were used, and the resulting mixtures were studied by oscillatory, steady-shear rheology, and the microstructure was probed by small-angle neutron scattering. The lengthening of the micelles and their entanglement result in remarkable viscoelastic properties, making rheology a useful tool to assess the effect of structural variations of the cosolutes on wormlike micelle formation. For a fixed concentration of CTAB and cosolute (200 mmol L(-1)), the relaxation time decreases in the following order: phenol > cinnamate> o-hydroxycinnamate > salicylate > o-methoxycinnamate > benzoate > o-methoxybenzoate. The variations in viscoelastic response are rationalized by using Mulliken population analysis to map out the electronic density of the cosolutes and quantify the barrier to rotation of specific groups on the aromatics. We find that the ability of the group attached to the aromatic ring to rotate is crucial in determining the packing of the cosolute at the micellar interface and thus critically impacts the micellar growth and, in turn, the rheological response. These results enable us for the first time to propose design rules for the self-assembly of the surfactants and cosolutes resulting in the formation of wormlike micelles with the cationic surfactant CTAB.

Effect Of Daily Use Of An Enzymatic Denture Cleanser On Candida Albicans Biofilms Formed On Polyamide And Poly(methyl Methacrylate) Resins: An In Vitro Study.

Candida biofilms on denture surfaces are substantially reduced after a single immersion in denture cleanser. However, whether this effect is maintained when dentures are immersed in cleanser daily is unclear. The purpose of this study was to evaluate the effect of the daily use of enzymatic cleanser on Candida albicans biofilms on denture base materials. The surfaces of polyamide and poly(methyl methacrylate) resin specimens (n=54) were standardized and divided into 12 groups (n=9 per group), according to study factors (material type, treatment type, and periods of treatment). Candida albicans biofilms were allowed to form over 72 hours, after which the specimens were treated with enzymatic cleanser once daily for 1, 4, or 7 days. Thereafter, residual biofilm was ultrasonically removed and analyzed for viable cells (colony forming units/mm(2)) and enzymatic activity (phospholipase, aspartyl-protease, and hemolysin). Factors that interfered with the response variables were analyzed by 3-way ANOVA with the Holm-Sidak multiple comparison method (α=.05). Polyamide resin presented more viable cells of Candida albicans (P<.001) for both the evaluated treatment types and periods. Although enzymatic cleansing significantly (P<.001) reduced viable cells, daily use did not maintain this reduction (P<.001). Phospholipase activity significantly increased with time (P<.001) for both materials and treatments. However, poly(methyl methacrylate) based resin (P<.001) and enzymatic cleansing treatment (P<.001) contributed to lower phospholipase activity. Aspartyl-protease and hemolysin activities were not influenced by study factors (P>.05). Although daily use of an enzymatic cleanser reduced the number of viable cells and phospholipase activity, this treatment was not effective against residual biofilm over time.

Sensory evaluation of black instant coffee beverage with some volatile compounds present in aromatic oil from roasted coffee

The oil obtained from Brazilian roasted coffee by supercritical CO2 extraction shows considerable aromatic properties, mainly composed by five aromatic compounds, 2-methylpyrazine; 2-furfurylalcohol, 2,5-dimethylpyrazine; γ-butyrolactone and 2-furfurylacetate. Sensory analyses were used to verify the influence of a mixture of these important classes of aromatic coffee compounds (pyrazines, furans and lactones) and of the roasted coffee aromatic oil on the coffee aroma and flavour of black instant freeze and spray-dried coffee beverages. In the acceptance evaluation of the aroma, the samples prepared with freeze-dried instant coffee without the mixture of volatile compounds (sample 4) were not significantly different from the freeze-dried instant coffee in which the aromatic coffee oil was added (sample 5) and from the sample prepared with freeze-dried coffee in which the mixture of the five volatile was added (sample 3), coincidentally from the same drying process. Therefore, sample (3) did not differ from samples prepared with spray dried instant coffee without (sample 1) and to which (sample 2) the mixture of volatile was added. Therefore, with respect to this attribute, the addition of this mixture did not interfere in this drink acceptance. Taking into consideration the flavor, samples prepared with freeze-dried instant coffee in which the aromatic coffee oil was added (5) and the samples with (3) and without (4) the mixture of the five volatile was added did not differ significantly, however sample (4) did not differ from samples (1) and (2). Regarding this attribute, the addition of the aromatic oil of roasted coffee or a mixture of volatile in samples of freeze-dried instant coffee had a better acceptance than those dried by spray dryer (1) and (2). Thus, the enrichment of drinks with the aromatic oil of roasted coffee, or even with the mixture of the five components did not influence the consumer acceptance with respect to the aroma, but exerts influence with respect to flavour.

Quantification and source identification of atmospheric particulate polycyclic aromatic hydrocarbons and their dry deposition fluxes at three sites in Salvador Basin, Brazil, impacted by mobile and stationary sources

The present work has aimed to determine the 16 US EPA priority PAH atmospheric particulate matter levels present in three sites around Salvador, Bahia: (i) Lapa bus station, strongly impacted by heavy-duty diesel vehicles; (ii) Aratu harbor, impacted by an intense movement of goods, and (iii) Bananeira village on Maré Island, a non vehicle-influenced site with activities such as handcraft work and fisheries. Results indicated that BbF (0.130-6.85 ng m-3) is the PAH with highest concentration in samples from Aratu harbor and Bananeira and CRY (0.075-6.85 ng m-3) presented higher concentrations at Lapa station. PAH sources from studied sites were mainly of anthropogenic origin such as gasoline-fueled light-duty vehicles and diesel-fueled heavy-duty vehicles, discharges in the port, diesel burning from ships, dust ressuspension, indoor soot from cooking, and coal and wood combustion for energy production.