Milena Ginic-Markovic

Variation in performance of surfactant loading and resulting nitrate removal among four selected natural zeolites

Surfactant modified zeolites (SMZs) have the capacity to target various types of water contaminants at relatively low cost and thus are being increasingly considered for use in improving water quality. It is important to know the surfactant loading performance of a zeolite before it is put into application. In this work we compare the loading capacity of a surfactant, hexadecyltrimethylammonium bromide (HDTMA-Br), onto four natural zeolites obtained from specific locations in the USA, Croatia, China, and Australia. The surfactant loading is examined using thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, and Raman spectroscopy. We then compare the resulting SMZs performance in removing nitrate from water. Results show that TGA is useful to determine the HDTMA loading capacity on natural zeolites. It is also useful to distinguish between a HDTMA bi-layer and a HDTMA mono-layer on the SMZ surface, which has not been previously reported in the literature. TGA results infer that HDTMA (bi-layer) loading decreases in the order of US zeolite>Croatian zeolite>Chinese zeolite>Australian zeolite. This order of loading explains variation in performance of nitrate removal between the four SMZs. The SMZs remove 8-18 times more nitrate than the raw zeolites. SMZs prepared from the selected US and Croatian zeolites were more efficient in nitrate removal than the two zeolites commercially obtained from Australia and China.

Observation of the keto tautomer of d-fructose in D2O using 1H NMR spectroscopy

D-Fructose was analysed by NMR spectroscopy and previously unidentified (1)H NMR resonances were assigned to the keto and α-pyranose tautomers. The full assignment of shifts for the various fructose tautomers enabled the use of (1)H NMR spectroscopy in studies of the mutarotation (5-25°C) and tautomeric composition at equilibrium (5-50°C). The mutarotation of β-pyranose to furanose tautomers in D(2)O at a concentration of 0.18 M was found to have an activation energy of 62.6 kJmol(-1). At tautomeric equilibrium (20°C in D(2)O) the distribution of the β-pyranose, β-furanose, α-furanose, α-pyranose and the keto tautomers was found to be 68.23%, 22.35%, 6.24%, 2.67% and 0.50%, respectively. This tautomeric composition was not significantly affected by varying concentrations between 0.089 and 0.36 M or acidification to pH 3. Upon equilibrating at 6 temperatures between 5 and 50°C there was a linear relationship between the change in concentration and temperature for all forms.

Fine-Tuning the Surface of Forward Osmosis Membranes via Grafting Graphene Oxide: Performance Patterns and Biofouling Propensity

Graphene oxide (GO) nanosheets were attached to the polyamide selective layer of thin film composite (TFC) forward osmosis (FO) membranes through a poly L-Lysine (PLL) intermediary using either layer-by-layer or hybrid (H) grafting strategies. Fourier transform infrared spectroscopy, zeta potential, and thermogravimetric analysis confirmed the successful attachment of GO/PLL, the surface modification enhancing both the hydrophilicity and smoothness of the membranes surface demonstrated by water contact angle, atomic force microscopy, and transmission electron microscopy. The biofouling resistance of the FO membranes determined using an adenosine triphosphate bioluminescence test showed a 99% reduction in surviving bacteria for GO/PLL-H modified membranes compared to pristine membrane. This antibiofouling property of the GO/PLL-H modified membrane was reflected in reduced flux decline compared to all other samples when filtering brackish water under biofouling conditions. Further, the high density and tightly bound GO nanosheets using the hybrid modification reduced the reverse solute flux compared to the pristine, which reflects improved membrane selectivity. These results illustrate that the GO/PLL-H modification is a valuable addition to improve the performance of FO TFC membranes.

Analysis of the hydrolysis of inulin using real time 1H NMR spectroscopy

The hydrolysis of various carbohydrates was investigated under acidic conditions in real time by (1)H NMR spectroscopy, with a focus on the polysaccharide inulin. Sucrose was used as a model compound to illustrate the applicability of this technique. The hydrolysis of sucrose was shown to follow pseudo first order kinetics and have an activation energy of 107.0 kJ mol(-1) (SD 1.7 kJ mol(-1)). Inulin, pullulan and glycogen also all followed pseudo first order kinetics, but had an initiation phase at least partially generated by the protonation of the glycosidic bonds. It was also demonstrated that polysaccharide chain length has an effect on the hydrolysis of inulin. For short chain inulin (DPn 18, SD 0.70) the activation energy calculated for the hydrolytic cleavage of glucose was similar to sucrose at 108.5 kJ mol(-1) (SD 0.60). For long chain inulin (DPn 30, SD 1.3) the activation energy for the hydrolytic cleavage of glucose was reduced to 80.5 kJ mol(-1) (SD 2.3 kJ mol(-1)). This anomaly has been attributed to varied conformations for the two different lengths of inulin chain in solution.

Characterization of elastomer compounds by thermal analysis

Abstract Thermal analysis provides very useful tools for the characterization and identification of both, elastomer compound and finished product. This investigation focuses on the use of different thermal techniques for compositional analysis, characterization of thermal, oxidative stability and glass-transition temperature ( T g ) of different components present in the elastomeric systems. Thermogravimetry (TG) is critical for identification of composition. TG analysis of three compositions ( S 1 , S 2 and S 3 ) shows S 1 and S 2 are soft-oil extended compounds and S 3 is a hard compound, all comprising ethylene propylene diene rubber (EPDM). Energy dispersive X-ray analysis (EDAX) of the residues from TGA reveals the presence of mineral filler clay in sample ( S 3 ) besides carbon black. The use of high-resolution TG has been found to give better resolution between overlapping weight loss steps leading to better quantification of various components compared to conventional TG. The coefficient of expansion of the rubber compound (from thermo-mechanical analysis – TMA) above T g is correlated to the hardness of the samples. The use of differential scanning calorimetry (DSC) to determine oxidative stability identifies also the presence of similar antioxidants. Dynamic mechanical analysis (DMA) is found to be very sensitive for characterization of glass-transition temperature, visco-elastic properties and, in particular, the adhesion between the elastomer compound and coating.

Synthesis of Carbon Nanotube (CNT) Composite Membranes

Carbon nanotubes are attractive approach for designing of new membranes for advanced molecular separation because of their unique transport properties and ability to mimic biological protein channels. In this work the synthetic approach for fabrication of carbon nanotubes (CNTs) composite membranes is presented. The method is based on growth of multi walled carbon nanotubes (MWCNT) using chemical vapour deposition (CVD) on the template of nanoporous alumina (PA) membranes. The influence of experimental conditions including carbon precursor, temperature, deposition time, and PA template on CNT growth process and quality of fabricated membranes was investigated. The synthesis of CNT/PA composites with controllable nanotube dimensions such as diameters (30–150 nm), and thickness (5–100 μm), was demonstrated. The chemical composition and morphological characteristics of fabricated CNT/PA composite membranes were investigated by various characterisation techniques including scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDXS), high resolution transmission electron microscopy (HRTEM) and x-ray diffraction (XRD). Transport properties of prepared membranes were explored by diffusion of dye (Rose Bengal) used as model of hydrophilic transport molecule.

Aligned silane-treated MWCNT/liquid crystal polymer films

We report on a method to preferentially align multiwall carbon nanotubes (MWCNTs) in a liquid crystalline matrix to form stable composite thin films. The liquid crystalline monomeric chains can be crosslinked to form acrylate bridges, thereby retaining the nanotube alignment. Further post-treatment by ozone etching of the composite films leads to an increase in bulk conductivity, leading to higher emission currents when examined under conducting scanning probe microscopy. The described methodology may facilitate device manufacture where electron emission from nanosized tips is important in the creation of new display devices.

Single-Step Assembly of Multifunctional Poly(tannic acid)–Graphene Oxide Coating To Reduce Biofouling of Forward Osmosis Membranes

Graphene oxide (GO) nanosheets have antibacterial properties that have been exploited as a biocidal agent used on desalination membrane surfaces in recent research. Nonetheless, improved strategies for efficient and stable attachment of GO nanosheets onto the membrane surface are still required for this idea to be commercially viable. To address this challenge, we adopted a novel, single-step surface modification approach using tannic acid cross-linked with polyethylene imine as a versatile platform to immobilize GO nanosheets to the surface of polyamide thin film composite forward osmosis (FO) membranes. An experimental design based on Taguchis statistical method was applied to optimize the FO processing conditions in terms of water and reverse solute fluxes. Modified membranes were analyzed using water contact angle, adenosine triphosphate bioluminescence, total organic carbon, Fourier transform infrared spectroscopy, ζ potential, X-ray photoelectron spectroscopy, transmission electron microscopy, and atomic force microscopy. These results show that membranes were modified with a nanoscale (<10 nm), smooth, hydrophilic coating that, compared to pristine membranes, improved filtration and significantly mitigated biofouling by 33% due to its extraordinary, synergistic antibacterial properties (99.9%).

Compatibility studies between mannitol and omeprazole sodium isomers

Omeprazole, commonly used in the treatment of various gastrointestinal disorders degrades rapidly in acidic pHs and results in inter-individual variability due to different rates of metabolism amongst patients. Since S-omeprazole shows more predictable bioavailability and excipients have been known to interact with active pharmaceutical ingredients to produce altered bioavailability, it was decided to investigate the compatibility of omeprazole sodium isomers with mannitol, the major excipient in omeprazole formulations using differential scanning calorimetry (DSC) for bulk drug, attenuated total reflectance (ATR) infrared (IR) spectroscopy in a powder mixture and localized thermal analysis (LTA) from a drug disk. DSC results clearly indicate an interaction between mannitol and R-omeprazole sodium due to decreased melting temperatures and broadening peaks. The DSC of S-omeprazole sodium does not show melting temperature although the drug was crystalline. Because of the accelerated temperature conditions during DSC experiments applied in this work, ATR-IR was undertaken to determine whether these results occurred at room temperature for the solid dosage form. The ATR-IR results show a difference between R- and S-omeprazole sodium with mannitol by the appearance of both the amino (N-H) and imino (N-H) stretching frequencies for R-omeprazole and only the N-H for the S-omeprazole sodium. It may thus be concluded that different ratios for the tautomeric forms for S- and R-omeprazole sodium result in changes in the degree of crystallinity and are responsible for the interaction with mannitol, common excipient in formulation. These interactions may be directly related to the difference in terms of bioavailability.

Weatherability of coated EPDM rubber compound by controlled UV irradiation

Polymeric composites for automotive window seal applications are generally exposed to complex service environment conditions. The fundamental physico-chemical processes that control the durability of such composite systems on a micro and macroscopic level were evaluated in the present case using thermal analysis (TA), elemental mapping and microscopy. Five diAerent EPDM rubber compounds (control, three bulk modified and one surface modified), coated with polyurethane coating were exposed to controlled UV irradiation. The higher the adhesion, the less the extent of UV penetration through the interface. The photo-oxidation mainly takes place from the surface, as the energy gets consumed and the intensity of the UV decreases on its passage through the strongly adhered layers to the rubber compound. The coating layer being on the surface, is more aAected and photodegraded by UV irradiation than the rubber compound. The sample P1cc, being multiphasic in nature and with a strong interface, can scatter the UV strongly and hence shows best weatherability among all the systems. # 2000 Elsevier Science Ltd. All rights reserved.