Polymer microspheres: synthesis, characterisation and post-functionalisation by olefin metathesis

Porous polymer particles are used in an extraordinarily wide range of advanced and everyday applications, from combinatorial chemistry, solid-phase organic synthesis and polymer-supported reagents, to environmental analyses and the purification of drinking water. The installation and exploitation of functional chemical handles on the particles is often a prerequisite for their successful exploitation, irrespective of the application and the porous nature of the particles. New methodology for the chemical modification of macroreticular polymers is the primary focus of the work presented in this thesis. Porous polymer microspheres decorated with a diverse range of functional groups were synthesised by the post-polymerisation chemical modification of beaded polymers via olefin cross metathesis. The polymer microspheres were prepared by the precipitation polymerisation of divinylbenzene in porogenic (pore-forming) solvents; the olefin cross-metathesis (CM) functionalisation reactions exploited the pendent (polymer-bound) vinyl groups that were not consumed by polymerisation. Olefin CM reactions involving the pendent vinyl groups were performed in dichloromethane using second-generation Grubbs catalyst (Grubbs II), and a wide range of coupling partners used. The results obtained indicate that high quality, porous polymer microspheres synthesised by precipitation polymerisation in near-θ solvents can be functionalised by olefin CM under very mild conditions to install a diverse range of chemical functionalities into a common polydivinylbenzene precursor. Gel-type polymer microspheres were prepared by the precipitation copolymerisation reaction of divinylbenzene and allyl methacrylate in neat acetonitrile. The unreacted pendent vinyl groups that were not consumed by polymerisation were subjected to internal and external olefin metathesis-based hypercrosslinking reactions. Internal hypercrosslinking was carried out by using ring-closing metathesis (RCM) reactions in toluene using Grubbs II catalyst. Under these conditions, hypercrosslinked (HXL) polymers with specific surface areas around 500 m2g-1 were synthesised. External hypercrosslinking was attempted by using CM/RCM in the presence of a multivinyl coupling partner in toluene using second-generation Hoveyda-Grubbs catalyst. The results obtained indicate that no HXL polymers were obtained. However, during the development of this methodology, a new type of polymerisation was discovered with tetraallylorthosilicate as monomer.

Non chemical natural organic matter removal with a contact TiO2 process

Dissertação de Mestrado, Tecnologia dos Alimentos, Instituto Superior de Engenharia, Universidade do Algarve, 2014

Conjugated polymer nanoparticles for biological labeling and delivery

Cancer remains one of the world’s most devastating diseases, with more than 10 million new cases every year. However, traditional treatments have proven insufficient for successful medical management of cancer due to the chemotherapeutics’ difficulty in achieving therapeutic concentrations at the target site, non-specific cytotoxicity to normal tissues, and limited systemic circulation lifetime. Although, a concerted effort has been placed in developing and successfully employing nanoparticle(NP)-based drug delivery vehicles successfully mitigate the physiochemical and pharmacological limitations of chemotherapeutics, work towards controlling the subcellular fate of the carrier, and ultimately its payload, has been limited. Because efficient therapeutic action requires drug delivery to specific organelles, the subcellular barrier remains critical obstacle to maximize the full potential of NP-based delivery vehicles. The aim of my dissertation work is to better understand how NP-delivery vehicles’ structural, chemical, and physical properties affect the internalization method and subcellular localization of the nanocarrier. ^ In this work we explored how side-chain and backbone modifications affect the conjugated polymer nanoparticle (CPN) toxicity and subcellular localization. We discovered how subtle chemical modifications had profound consequences on the polymer’s accumulation inside the cell and cellular retention. We also examined how complexation of CPN with polysaccharides affects uptake efficiency and subcellular localization. ^ This work also presents how changes to CPN backbone biodegradability can significantly affect the subcellular localization of the material. A series of triphenyl phosphonium-containing CPNs were synthesized and the effect of backbone modifications have on the cellular toxicity and intracellular fate of the material. A mitochondrial-specific polymer exhibiting time-dependent release is reported. Finally, we present a novel polymerization technique which allows for the controlled incorporation of electron-accepting benzothiadiazole units onto the polymer chain. This facilitates tuning CPN emission towards red emission. ^ The work presented here, specifically, the effect that side-chain and structure, polysaccharide formulation and CPN degradability have on material’s uptake behavior, can help maximize the full potential of NP-based delivery vehicles for improved chemotherapeutic drug delivery.^

Synthesis of novel organic semiconductors for optoelectronic devices

This thesis describes the synthesis and characterisation of novel conjugated organic materials with optoelectronic application. The first chapter provides an introduction about organic semiconductors and in particular about their working principle from a physical and chemical point of view. An overview of the most common types of solar cells is provided, including examples of some of the best performing materials. The second chapter describes the synthesis of a new library of flavin derivatives as potential active materials for optoelectronic applications. Flavins are natural redox-active molecules, which show potential application in optoelectronics, thanks to their stability and versatility. FPF-Flavins, for instance, could be used either as acceptor units in push-pull polyconjugated systems or as acceptor unit in dyes for DSSCs. In the same chapter a first attempt of synthesising bis-flavins to be used as N-type semiconductors in BHJ devices is described. The third chapter describes the successful synthesis and characterization of a series of conjugated organic molecules based on the benzothiadiazole moiety. Among these, three molecules containing ferrocene as donor unit were tested as sensitizers for DSSCs, reporting a PCE of 0.3% as the best result. Further studies indicated a significant problem of charge recombination which limits the performance. A near-infrared absorbing push-pull polymer, based on BbT as acceptor unit, was also synthesised and tested in BHJ devices as P-type semiconductor in blend with PC71BM, showing a VOC of 0.71 V. Finally, the last chapter describes the synthesis of several tetrathiafulvalene derivatives in order to explore this moiety as donor unit in dyes for DSSCs and as HTM for perovskite-based solar cells. In particular, two very simple dyes were synthesised and implemented in DSSCs reporting a PCE 0.2% and 0.4%, respectively. The low efficiency was associated to the tendency to aggregate at the solid state, with the absorption shifting from the visible to the infrared range. A conjugated molecule, containing a DPP core, was also synthesised and tested as HTM for perovskite solar cells. The best reported PCE of 7.7% was obtained without any additives. A case study about dehalogenation and “halogen dance” in TTF iodide is also presented.

Synthesis of new non-fullerene acceptors based on indacenodithiophene core for organic solar cells

Due to the low cost, lightness and flexibility, Polymer Solar Cell (PSC) technology is considered one of the most promising energy technologies. In the past decades, PSCs using fullerenes or fullerene derivatives as the electron acceptors have made great progress with best power conversion efficiency (PCE) reaching 11%. However, fullerene type electron acceptors have several drawbacks such as complicated synthesis, a low light absorption coefficient and poor tuning in energy levels, which prevent the further development of fullerene-based PSCs. Hence the need to have a new class of electron acceptors as an alternative to conventional fullerene compounds. Non-fullerene acceptors (NFAs) have developed rapidly in the last years and the maximum PCEs have exceeded 14% for single-junction cells and 17% for double-junction tandem cells. By combining an electron-donating backbone, generally with several fused rings with electron-withdrawing units, we can simply construct NFA of the acceptor–donor–acceptor type (A–D–A). Versatile molecular structures have been developed using methods such as acceptor motif engineering and donor motif engineering. However, there are only a few electron-donating backbones that have been proved to be successful. Therefore, it is still necessary to develop promising building blocks to further enrich the structural diversity. An indacenodithiophene (IDT) unit with just five fused rings has a sufficiently rigid coplanar structure, which has been regarded as one of the promising electron-rich units to design high-performance A–D–A NFAs. In this work, performed at the King Abdullah University of Science and Technology in Saudi Arabia, a new nine-cyclic building block (TBIDT) with a two benzothiophene unit was synthesized and used for designing new non-fullerene electron acceptors.

Study of the absorption of organic compounds on biopolymers

This work has been conducted in order to determine the solubility and diffusion coefficients of different aromatic substances in two different grades of polylactic acid (PLA), Amorphous (PDLLA) and Crystalline (PLLA); in particular the focus is on the following terpenes: Linalool, α-Pinene, β-Citronellol and L-Linalool. Moreover, further analyses have been carried out with the aim to verify if the use of neat crystalline PLA, (PLLA), a chiral substrate, may lead to an enantioenrichment of absorbed species in order to use it as membrane in enantioselective processes. The other possible applications of PLA, which has aroused interest in carry out the above-mentioned work, concerns its use in food packaging. Therefore, it is interesting and also very important, to evaluate the barrier properties of PLA, focusing in particular on the transport and absorption of terpenes, by the packaging and, hence, by the PLA. PLA films/slabs of one-millimeter thickness and with square shape, were prepared through the Injection Molding process. On the resulting PLA films heat pretreatment processes of normalizing were then performed to enhance the properties of the material. In order to evaluate solubility and diffusion coefficient of the different penetrating species, the absorption kinetics of various terpenes, in the two different types of PLA, were determined by gravimetric methods. Subsequently, the absorbed liquid was extracted with methanol (MeOH), non- solvent for PLA, and the extract analyzed by the use of High Performance Liquid Chromatography (HPLC), in order to evaluate its possible enantiomeric excess. Moreover, PLA films used were subjected to differential scanning calorimetry (DSC) which allowed to measure the glass transition temperature (Tg) and to determine the degree of crystallinity of the polymer (Xc).

Design of luminescent metal complexes for polymer science

The program of my PhD studies has been dealing with the investigation of the research outcomes that may result from the use of luminescent Iridium(III) cyclometalated complexes in the field of polymer science. In particular, my activity has been focused on exploring two main applicative contexts, i.e. Ir(III) complexes for preparing polymers and in combination with polymers. In the first part, a new set of luminescent Ir(III) complexes was exploited as photocatalysts for light-assisted atom transfer radical polymerization of methyl methacrylate. The decoration of both cyclometalated and ancillary ligands with sp3 hybridized nitrogen substituents together with the use of specific counterions, imparted suitable photophysical and redox properties for an efficient photocatalyzed process. The second part has been focused on the employment of Ir(III) tetrazole complexes as phosphorescent dyes in polymeric materials. Colourless luminescent solar concentrators were prepared blending two Ir(III) cyclometalates with acrylate polymers. Their performances were investigated, leading to promising outcomes comparable, or superior, to those obtained from colourless LSCs based on organic fluorophores. As a complementary approach, Ir(III) complexes were covalently linked to polymers in the side chain, to obtain a new class of metallopolymers. To this extent, a bifunctional tetrazolate molecule, equipped with a coordination site and a polymerizable unit, was designed. The photophysical properties of the resultant luminescent polymeric films were discussed. In the end, an additional project involving both polymers and metal compounds was carried out during my experience as a visiting PhD student at Humboldt – University of Berlin. Polystyrene and polyethylene glycol -based ion-exchange resins were functionalized with peptides through a ligation pathway, for the selective chelation of Copper(II) in aqueous solutions. The coordinating capability of the materials towards Cu2+ ions was tested by ICP-MS analysis. The resins strategically modified with ion-selective peptides, may be exploited in the preparation of water-processing devices.

Nanocomposites based on poly(caprolactone)-chitosan electrospun nanofibers and metallic oxide nanoparticles. Their potential use to adsorption and photocatalytic degradation of organic contaminants

Pollution of water bodies is one of the most common environmental problems today. Organic pollutants are one of the main drawbacks in this natural resource, among which the following stand out long-lived dyes, pharmaceuticals, and pesticides. This research aims at obtaining nanocomposites based on polycaprolactone-chitosan (PCL-CS) electrospun nanofibers (NFs) containing TiO2 nanoparticles (NPs) for the adsorption and photocatalytic degradation of organic pollutants, using Rhodamine B as a model. The fabricated hybrid materials were characterized by FT-IR, TGA, DSC, SEM, TEM, tensile properties, and the contact angle of water drops. The photoactivity of the NFs was investigated using a batch-type system by following UV-Vis absorbance and fluorescence of rhodamine B (RhB). For this purpose, TiO2NPs were successfully ex-situ incorporated into the polymer matrix promoting good mechanical properties and higher hydrophilicity of the material. The results showed that CS in the NFs increased the absorption and degradation of RhB by the TiO2NPs. CS attracted the pollutant molecules to the active sites vicinity of TiO2NPs, favoring initial adsorption and degradation. In other words, a bait-hook-and-destroy effect was evidenced. It also was demonstrated that the sensitization of TiO2 by organic dyes (e.g., perylene derivative) considerably improves the photocatalytic activity under visible radiation, allowing the use of low amounts of TiO2. (≈0.05 g/1 g of fiber). Hence, the current study is expected to contribute with an environmentally friendly green alternative solution.

Engineered Nanoparticles And Organic Matter: A Review Of The State-of-the-art.

Growth in the development and production of engineered nanoparticles (ENPs) in recent years has increased the potential for interactions of these nanomaterials with aquatic and terrestrial environments. Carefully designed studies are therefore required in order to understand the fate, transport, stability, and toxicity of nanoparticles. Natural organic matter (NOM), such as the humic substances found in water, sediment, and soil, is one of the substances capable of interacting with ENPs. This review presents the findings of studies of the interaction of ENPs and NOM, and the possible effects on nanoparticle stability and the toxicity of these materials in the environment. In addition, ENPs and NOM are utilized for many different purposes, including the removal of metals and organic compounds from effluents, and the development of new electronic sensors and other devices for the detection of active substances. Discussion is therefore provided of some of the ways in which NOM can be used in the production of nanoparticles. Although there has been an increase in the number of studies in this area, further progress is needed to improve understanding of the dynamic interactions between ENPs and NOM.

The Influence Of The Buffering Capacity On The Production Of Organic Acids And Alcohols From Wastewater In Anaerobic Reactor.

Some bacteria common in anaerobic digestion process can ferment a broad variety of organic compounds to organic acids, alcohols, and hydrogen, which can be used as biofuels. Researches are necessary to control the microbial interactions in favor of the alcohol production, as intermediary products of the anaerobic digestion of organic compounds. This paper reports on the effect of buffering capacity on the production of organic acids and alcohols from wastewater by a natural mixed bacterial culture. The hypothesis tested was that the increase of the buffering capacity by supplementation of sodium bicarbonate in the influent results in benefits for alcohol production by anaerobic fermentation of wastewater. When the influent was not supplemented with sodium bicarbonate, the chemical oxygen demand (COD)-ethanol and COD-methanol detected in the effluent corresponded to 22.5 and 12.7 % of the COD-sucrose consumed. Otherwise, when the reactor was fed with influent containing 0.5 g/L of sodium bicarbonate, the COD-ethanol and COD-methanol were effluents that corresponded to 39.2 and 29.6 % of the COD-sucrose consumed. Therefore, the alcohol production by supplementation of the influent with sodium bicarbonate was 33.6 % higher than the fermentation of the influent without sodium bicarbonate.

A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopolímeros na remoção catiônica

This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.

Impact and fracture resistance of an experimental acrylic polymer with elastomer in different proportions

The purpose of this study was to evaluate the impact and fracture resistance of acrylic resins: a heat-polymerized resin, a high-impact resin and an experimental polymethyl methacrylate with elastomer in different proportions (10, 20, 40 and 60%). 120 specimens were fabricated and submitted to conventional heat-polymerization. For impact test, a Charpy-type impact tester was used. Fracture resistance was assessed with a 3-point bending test by using a mechanical testing machine. Ten specimens were used for each test. Fracture (MPa) and impact resistance values (J.m-1) were submitted to ANOVA - Bonferroni's test - 5% significance level. Materials with higher amount of elastomer had statistically significant differences regarding to impact resistance (p < 0.05). Fracture resistance was superior (p < 0.01) for high-resistance acrylic resin. The increase in elastomer concentration added to polymethyl methacrylate raised the impact resistance and decreased the fracture resistance. Processing the material by injection decreased its resistance to impact and fracture.

Ambiental volatile organic compounds in the megacity of São Paulo

In order to characterize the composition of the main urban air organic compounds in the megacity of Sao Paulo, analysis of samples collected during the winter of 2003 downtown was carried out. The samplings were performed on the roof of a building in the commercial center of São Paulo. Hydrocarbons and carbonyls compounds were collected on August 4, 5 and 6. Comparing to previous data, the concentration of hydrocarbons presented no decrease in the concentration, except for the aldehydes, which decreased when compared to previous data. Among the HCs species analyzed, the highest concentrations observed were those of toluene (7.5 ± 3.4 ppbv), n-decane (3.2 ± 2.0 ppbv), benzene (2.7 ± 1.4 ppbv) and 1,3,5-trimethylbenzene (2.2 ± 1.5 ppbv).

Screening process for activity determination of conductive oxide electrodes for organic oxidation

A modified method for the calculation of the normalized faradaic charge (q fN) is proposed. The method involves the simulation of an oxidation process, by cyclic voltammetry, by employing potentials in the oxygen evolution reaction region. The method is applicable to organic species whose oxidation is not manifested by a defined oxidation peak at conductive oxide electrodes. The variation of q fN for electrodes of nominal composition Ti/RuX Sn1-X O2 (x = 0.3, 0.2 and 0.1), Ti/Ir0.3Ti0.7O2 and Ti/Ru0.3Ti0.7O2 in the presence of various concentrations of formaldehyde was analyzed. It was observed that electrodes containing SnO2 are the most active for formaldehyde oxidation. Subsequently, in order to test the validity of the proposed model, galvanostatic electrolyses (40 mA cm-2) of two different formaldehyde concentrations (0.10 and 0.01 mol dm-3) were performed. The results are in agreement with the proposed model and indicate that this new method can be used to determine the relative activity of conductive oxide electrodes. In agreement with previous studies, it can be concluded that not only the nature of the electrode material, but also the organic species in solution and its concentration are important factors to be considered in the oxidation of organic compounds.

Evaluation of capillaries with different inner coatings for DNA analysis using dilute polymer solutions by capillary electrophoresis

In this work three capillary columns, one with uncoated inner wall and two with covalently-bound internal coatings - poly(vinyl alcohol) (PVA) and poly(dimethylacrylamide) (PDMA) - both covalently covered - were used to separate DNA fragments and compared to DNA separation using replaceable polymer solutions. The separations were performed using hydroxyethylcellulose (HEC) (90-105 kDa) in concentrations ranging from 0.00 to 2.00% m/v. The results indicated that the separation efficiency was higher in the PVA capillary than in the PDMA in all evaluated concentrations of HEC. In addition, higher resolution was also observed in PVA-coated capillary since in PDMA the shape of the peaks was not reproducible when subsequent runs were performed. Contrary to what has previously been reported in the literature, no reasonable separation was possible in bare fused silica.