Described herein are three projects centered on the synthesis of conducting polymer derivatives for various applications. The first is the novel synthesis of 9,9-dioctylfluorene-co-benzothiadiazole [F8BT] oligomers through solid phase synthesis for the study of the thermodynamics and kinetics of electron transfer in the polymer. The second endeavor involves the synthesis of a series of 4”,3’’’-dialkyl-2,2’:5’,2”:5”,2’’’:5’’’,2’’’’:5’’’’,2’’’’’-sexithiophenes for the studies on crystal packing and surface deposition of organic p-type semiconducting materials. Lastly is described the development of a conducting metallopolymer based on the ligand 2,6-Bis(4-(2,2’-bithiophen-5-yl)-1H-pyrazol-1-yl)pyridine for use in a drug delivery system. / text

Orientador: Marcos Fernando de Souza Teixeira / Banca: Ana Maria Pires / Banca: Antonio Carlos Dias Angelo / Resumo: A formação de filmes poliméricos contendo azobenzeno tem recebido atenção especial devido à sua aplicação em dispositivos fotônicos. Neste trabalho estudamos a eletropolimerização de Bismarck Brown R (4-3- (2,4-diamin-5-metilfenil)- 4-metilfenildiazenil]diazenil-6-metilbenzeno-1,3-diamindiclorohidrato), filmes ultra-finos sobre substratos de ITO. Foi realizado o estudo do comportamento do filme polimérico variando-se parâmetros durante a etapa de eletropolimerização para a otimização do poliBBR, visando o desenvolvimento de eletrodos modificados para serem utilizados como sensores químicos. O uso da técnica eletroquímica na preparação de filmes poliméricos tem diversas vantagens, tais como a formação do filme diretamente sobre diferentes substratos, controle de espessura do filme, alta reprodutibilidade, geração de polímeros dopados e possibilidade de imobilização de espécies durante a fase de polimerização. Os filmes ultra-finos depositados nos substratos condutores por eletropolimerização foram caracterizados eletroquimicamente (voltametria cíclica e pulso diferencial), espectroscopia de ultravioleta-visível e microscopia de força atômica (AFM). O trabalho se destaca por possuir pouco ou nenhum relato na literatura sobre os dados obtidos dos estudos eletroquímicos e ópticos do comportamento do polímero de Bismarck Brown R. Foram obtidos dados interessantes no comportamento óptico no estudo da imobilização de íons metálicos na estrutura polimérica do BBR, destacando-se as diferentes geometrias e conformações (cis e trans) investigadas no trabalho / Abstract: The formation of azobenzeno containing polymeric films have been special attention due to its application in photonic devices. In this work we studied the electropolymerization of Bismarck Brown R (4-3-(2,4-diamin-5-methylphenyl)-4-methylphenyldiazenyl]diazenyl-6-methilbenzene-1,3-diamindiclorohidrato), ultra thin films on substrates of ITO. Was carried out study the behavior of the polymer film varying the parameters during the step for the electropolymerization polyBBR optimization, in order to develop modified electrodes to be used as chemical sensors. The use of electrochemical technique for preparing polymer films have several advantages, such as film formation directly on different substrates, film thickness control, high reproducibility, generating doped polymers and possible immobilization of species during the polymerization. The ultra-thin films deposited in conductive substrates were characterized electrochemically (cyclic voltammetry and differential pulse), UV-Vis spectroscopy and atomic force microscopy (AFM). The work stands out due to little or no reports in the literature on data obtained from studies of the electrochemical and optical behavior of polymer Bismarck Brown R. We obtained interesting data on optical behavior in the study immobilization of metal ion in the polymeric structure of the BBR, highlighting the different geometries and conformations (cis and trans) investigated in the work / Mestre

As galectinas são proteínas que se ligam a -galactosídeos por meio do domínio de reconhecimento de carboidratos (CRD do inglês, Carbohydrate Recognition Domain) e que participam de vários processos de reconhecimento celular, sinalização, adesão e destinação intracelular de proteínas recém-sintetizadas. A primeira galectina, Galectina-1 (Gal-1), foi identificada em 1976 e possui um papel importante na progressão e proliferação tumoral, angiogênese, resistência a drogas e processos inflamatórios. Assim, é interessante a construção de dispositivos com Galectinas imobilizadas, preservando o CRD para o estudo de mecanismos e/ou detecção destas doenças. Neste trabalho a produção e caracterização de uma proteína recombinante fusionada, a MBP-Gal-1, foi descrita. A proposta do projeto foi pautada na hipótese de que a fusão da MBP à Gal-1 seria uma excelente estratégia para imobilização orientada da proteína de interesse, (Gal-1), sobre eletrodos modificados com filme polimérico, auxiliando na preservação da atividade da biomolécula imobilizada para posterior desenvolvimento de biossensor. A MBP-Gal-1 foi purificada utilizando 2 colunas com resinas diferentes: sepharose/lactose e amilose onde foi possível comprovar a atividade/preservação dos sítios ativos da Gal-1 e MBP, respectivamente. A proteína fusionada teve seu estado oligomérico estimado e seu raio hidrodinâmico determinado pela técnica Espalhamento Dinâmico da Luz sendo que a mesma se encontrava na forma monomérica com raio hidrodinâmico de 4 nm ± 1,26. A massa molecular de 57,834 kDa para a MBP-Gal-1 foi obtida através da técnica de Espectrometria de Massas MALDI-TOF/TOF. O PPB, material polimérico empregado na modificação dos eletrodos de carbono vítreo e ouro, foi sintetizado e teve sua estrutura confirmada pela técnica de Ressonância Magnética Nuclear; este material foi utilizado para a realização dos ensaios de Espectroscopia de Impedância Eletroquímica (EIE) e Ressonância de Plásmons de Superfície (SPR) para a construção do biossensor. Os ensaios EIE utilizando eletrodo de carbono vítreo modificado com PPB mostraram a importância da imobilização orientada da sonda (MBP-Gal-1) para garantir a preservação da atividade biológica da mesma, uma vez que os resultados relativos ao aumento da Resistência à Transferência de Carga (Rtc), após adição do alvo (lactose), foram da ordem de 80% a mais para a proteína fusionada MBP-Gal-1 quando comparados à proteína nativa Gal-1. Os ensaios de SPR revelaram maior SPR efetiva para a MBP-Gal-1 imobilizada sobre superfície de eletrodo Au-SPR modificado com PPB o qual apresentou bom desempenho na detecção de lactose. / Galectins are proteins that bind to -galactosides by the Carbohydrate Recognition Domain (CRD) and participate in various processes of cell recognition, signaling, adhesion and intracellular destination of newly synthesized proteins. The first galectin, Galectin-1 (Gal-1), was identified in 1976 and plays an important role in tumor progression and proliferation, angiogenesis, drug resistance and inflammatory processes. Thus, it is interesting to desing devices with immobilized Galectins, preserving its CRD for the study of mechanisms and /or detection of such diseases. In this work the production and characterization of a fused recombinant protein, MBP-Gal-1, has been described. The project goal was based on the hypothesis that the fusion of the MBP to Gal-1 would be an excellent strategy for oriented immobilization of the protein of interest, (Gal-1), onto PPB- modified electrodes, promoting the preservation of the biomolecule activity immobilized for further development of a biosensor. MBP-Gal-1 was purified using 2 columns with different resins: sepharose/lactose and amylose and it was possible to prove the activity/preservation of both CRDs from Gal-1 and MBP, respectively. Dynamic Light Scattering showed that MBP-Gal-1 was in a monomeric form and with a hydrodynamic radius of 4 nm ± 1,26. The molecular mass of 57.834 kDa for MBP-Gal-1 was obtained by the technique of MALDI-TOF/TOF Mass Spectrometry. The PPB, a polymeric material used in the modification of glassy carbon and gold electrodes, was synthesized and its structure was confirmed by the Nuclear Magnetic Resonance (NMR); this material was used to carry out the Electrochemical Impedance Spectroscopy (EIS) and Surface Plasmon Resonance (SPR) tests for the construction of the biosensor. EIS assays using PPB-modified glassy carbon electrode showed the importance of probe-immobilization (MBP-Gal-1) to ensure the preservation of the biological activity of the protein, since the results related to the increase in Resistance of Charge Transfer (Rct), after addition of the target (lactose), were 80% higher for the fused protein MBP-Gal-1 when compared to the Gal-1 native-form protein. The SPR assays revealed a greater effective SPR for MBP-Gal-1 immobilized onto PPB-modified Au-SPR electrode surface which showed good performance in the detection of lactose.

As galectinas são proteínas que se ligam a -galactosídeos por meio do domínio de reconhecimento de carboidratos (CRD do inglês, Carbohydrate Recognition Domain) e que participam de vários processos de reconhecimento celular, sinalização, adesão e destinação intracelular de proteínas recém-sintetizadas. A primeira galectina, Galectina-1 (Gal-1), foi identificada em 1976 e possui um papel importante na progressão e proliferação tumoral, angiogênese, resistência a drogas e processos inflamatórios. Assim, é interessante a construção de dispositivos com Galectinas imobilizadas, preservando o CRD para o estudo de mecanismos e/ou detecção destas doenças. Neste trabalho a produção e caracterização de uma proteína recombinante fusionada, a MBP-Gal-1, foi descrita. A proposta do projeto foi pautada na hipótese de que a fusão da MBP à Gal-1 seria uma excelente estratégia para imobilização orientada da proteína de interesse, (Gal-1), sobre eletrodos modificados com filme polimérico, auxiliando na preservação da atividade da biomolécula imobilizada para posterior desenvolvimento de biossensor. A MBP-Gal-1 foi purificada utilizando 2 colunas com resinas diferentes: sepharose/lactose e amilose onde foi possível comprovar a atividade/preservação dos sítios ativos da Gal-1 e MBP, respectivamente. A proteína fusionada teve seu estado oligomérico estimado e seu raio hidrodinâmico determinado pela técnica Espalhamento Dinâmico da Luz sendo que a mesma se encontrava na forma monomérica com raio hidrodinâmico de 4 nm ± 1,26. A massa molecular de 57,834 kDa para a MBP-Gal-1 foi obtida através da técnica de Espectrometria de Massas MALDI-TOF/TOF. O PPB, material polimérico empregado na modificação dos eletrodos de carbono vítreo e ouro, foi sintetizado e teve sua estrutura confirmada pela técnica de Ressonância Magnética Nuclear; este material foi utilizado para a realização dos ensaios de Espectroscopia de Impedância Eletroquímica (EIE) e Ressonância de Plásmons de Superfície (SPR) para a construção do biossensor. Os ensaios EIE utilizando eletrodo de carbono vítreo modificado com PPB mostraram a importância da imobilização orientada da sonda (MBP-Gal-1) para garantir a preservação da atividade biológica da mesma, uma vez que os resultados relativos ao aumento da Resistência à Transferência de Carga (Rtc), após adição do alvo (lactose), foram da ordem de 80% a mais para a proteína fusionada MBP-Gal-1 quando comparados à proteína nativa Gal-1. Os ensaios de SPR revelaram maior SPR efetiva para a MBP-Gal-1 imobilizada sobre superfície de eletrodo Au-SPR modificado com PPB o qual apresentou bom desempenho na detecção de lactose. / Galectins are proteins that bind to -galactosides by the Carbohydrate Recognition Domain (CRD) and participate in various processes of cell recognition, signaling, adhesion and intracellular destination of newly synthesized proteins. The first galectin, Galectin-1 (Gal-1), was identified in 1976 and plays an important role in tumor progression and proliferation, angiogenesis, drug resistance and inflammatory processes. Thus, it is interesting to desing devices with immobilized Galectins, preserving its CRD for the study of mechanisms and /or detection of such diseases. In this work the production and characterization of a fused recombinant protein, MBP-Gal-1, has been described. The project goal was based on the hypothesis that the fusion of the MBP to Gal-1 would be an excellent strategy for oriented immobilization of the protein of interest, (Gal-1), onto PPB- modified electrodes, promoting the preservation of the biomolecule activity immobilized for further development of a biosensor. MBP-Gal-1 was purified using 2 columns with different resins: sepharose/lactose and amylose and it was possible to prove the activity/preservation of both CRDs from Gal-1 and MBP, respectively. Dynamic Light Scattering showed that MBP-Gal-1 was in a monomeric form and with a hydrodynamic radius of 4 nm ± 1,26. The molecular mass of 57.834 kDa for MBP-Gal-1 was obtained by the technique of MALDI-TOF/TOF Mass Spectrometry. The PPB, a polymeric material used in the modification of glassy carbon and gold electrodes, was synthesized and its structure was confirmed by the Nuclear Magnetic Resonance (NMR); this material was used to carry out the Electrochemical Impedance Spectroscopy (EIS) and Surface Plasmon Resonance (SPR) tests for the construction of the biosensor. EIS assays using PPB-modified glassy carbon electrode showed the importance of probe-immobilization (MBP-Gal-1) to ensure the preservation of the biological activity of the protein, since the results related to the increase in Resistance of Charge Transfer (Rct), after addition of the target (lactose), were 80% higher for the fused protein MBP-Gal-1 when compared to the Gal-1 native-form protein. The SPR assays revealed a greater effective SPR for MBP-Gal-1 immobilized onto PPB-modified Au-SPR electrode surface which showed good performance in the detection of lactose.

Within the framework of this thesis, three innovative electrochemical devices have been studied. A part of the work is devoted to an already existing device, laminates which are debonded by the application of a voltage. This type of material can potentially be used in a wide range of applications, including adhesive joints in vehicles to both reduce the total weight and to simplify the disassembly after end-of-life, enabling an inexpensive recycling process. Although already a functioning device, the development and tailoring of this process was slowed by a lack of knowledge concerning the actual electrochemical processes responsible for the debonding. The laminate studied consisted of an epoxy adhesive, mixed with an ionic liquid, bonding two aluminium foils. The results showed that the electrochemical reaction taking place at the releasing anode interface caused a very large increase in potential during galvanostatic polarization. Scanning electron microscopy images showed reaction products growing out from the electrode surface into the adhesive. These reaction products were believed to cause the debonding through swelling of the anodic interface so rupturing the adhesive bond. The other part of the work in this thesis was aimed at innovative lithium ion (Li‑ion) battery concepts. Commercial Li-ion batteries are two-dimensional thin film constructions utilized in most often mechanically rigid products. Two routes were followed in this thesis. In the first, the aim was flexible batteries that could be used in applications such as bendable reading devices. For this purpose, nano-fibrillated cellulose was used as binder material to make flexible battery components. This was achieved through a water-based filtration process, creating flexible and strong papers. These paper-based battery components showed good mechanical properties as well as good rate capabilities during cycling. The drawback using this method was relatively low coulombic efficiencies believed to originate from side-reactions caused by water remnants in the cellulose structure. The second Li-ion battery route comprised an electrochemical process to coat carbon fibers, shown to perform well as negative electrode in Li-ion batteries, from a monomer solution. The resulting polymer coatings were ~500 nm thick and contained lithium ions. This process could be controlled by mainly salt content in the monomer solution and polarization time, yielding thin and apparently pin-hole free coatings. By utilizing the carbon fiber/polymer composite as integrated electrode and electrolyte, a variety of battery designs could possibly be created, such as three-dimensional batteries and structural batteries. / <p>QC 20130403</p>

The Knorr-Paal reaction of 1,4-di(2-thienyl)-1,4-butanedione with aniline to yield 1-phenyl-2,5-di(2-thienyl)-1H-pyrrole (PTP) was performed in the presence of catalytical amounts of p-toluenesulfonic acid (PTSA). Chemical polymerization of the monomer yielded a soluble polymer. Structures of both the monomer and the polymer were investigated by Nuclear Magnetic Resonance (1H and 13C NMR) and Fourier Transform Infrared (FTIR) Spectroscopy. The average molecular weight of the chemically synthesized polymer was determined by Gel Permeation Chromatography (GPC) as Mn = 7.2 x 103 g/mol. The electrochemical oxidative polymerization of PTP was carried out via potentiodynamic electrolysis in the presence of LiClO4, NaClO4 (1:1) being the supporting electrolyte in acetonitrile. Electrochemical copolymerization of PTP with 3,4-ethylenedioxythiophene (EDOT) was carried out in acetonitrile (ACN)/ NaClO4/LiClO4 (0.1M) solvent-electrolyte couple system via potentiodynamic electrolysis. Cyclic voltammetry was used to investigate electrochemical behavior of the monomer and redox reactions of conducting polymers. Conductivities of films of the polymers were measured by four-probe technique. Surface morphologies of the films were investigated by Scanning Electron Microscope (SEM). Electrochromic properties of the conducting polymers were investigated via spectroelectrochemistry, kinetic and colorimetry studies. Spectroelectrochemical analysis of P(PTP) revealed electronic transitions at 413, 600 and 900 nm corresponding to &amp / #960 / -&amp / #960 / * transition, polaron, and bipolaron band formations, respectively. The spectroelectrochemical behavior of the P(PTP-co-EDOT) in comparison to those of the respective homopolymers revealed solid evidence of copolymerization based upon the differences in the spectral signatures. Switching time of the polymers was evaluated by kinetic studies upon measuring the percent transmittance (%T) at the maximum contrast point. As an application, absorption/transmission type electrochromic devices with ITO/homopolymer(copolymer)/gel electrolyte/PEDOT/ITO configuration was constructed, where homopolymer (copolymer) and PEDOT functioned as the anodically and the cathodically coloring layers, respectively. Spectroelectrochemistry, switching ability and open circuit memory of the devices were investigated. The results revealed that these devices have good switching times, reasonable contrasts and optical memories.

A novel electroactive monomer 5,8-Di(1H-pyrrol-2-yl)-2, 3-di(thiophen-2-yl) quinoxaline (PTQ) was successfully synthesized via Stille Coupling reaction between quinoxaline and pyrrole. Nuclear magnetic resonance (1H NMR and 13C NMR) and Mass spectroscopy were used to characterize the monomer. The monomer was electrochemically polymerized in the presence of tetrabutylammonium perchlorate (TBAP) as supporting electrolyte in dichloromethane. Monomer reveals relatively low oxidation potential at +0.70V. Spectroelectrochemical behaviors and switching ability of homopolymer were investigated by UV-Vis spectroscopy and cyclic voltammetry. Two &amp / #960 / -&amp / #960 / * transitions were observed at 400 nm and 815 nm with a low band gap, 1.0 eV. Polymer possesses 66% optical contrast in the Near IR region, which may be promising in NIR electrochromic device applications. Spectroelectrochemical behaviors and switching ability of copolymers were investigated by UV-Vis spectroscopy and cyclic voltammetry. Copolymers of PTQ in the presence of BiEDOT and BEBT were synthesized via potentiodynamic method in DCM/TBAP (0.1 M) solvent-electrolyte couple. P(PTQ-co-BiEDOT) reveals oxidation potential at +0.45V, whereas P(PTQ-co-BEBT) reveals oxidation potential at +0.70V. The spectroelectrochemical behavior of the P(PTQ-co-BiEDOT) and P(PTQ-co-BEBT) in comparison to homopolymer revealed solid evidence of copolymerization based upon the differences in the spectral signatures. Switching time of the polymers was evaluated by kinetic studies upon measuring the percent transmittance (%T) at the maximum contrast point.

Conducting metallopolymers have been investigated for a variety of applications due to their ability to take advantage of both the mechanical processability of the polymer material, as well as the optical and electronic properties of the metal. Our project goal is to design, synthesize and characterize novel iridium(III)-containing conducting metallopolymers for use as the active layer in polymer light-emitting diodes. We have utilized thiophene functionalized ligands that can be readily electropolymerized into conducting polymer thin films and can be easily incorporated into a device structure. Iridium(III) was chosen as the metal center due to its promising photophysical properties, as similar complexes have demonstrated high luminescent quantum yields and short phosphorescent lifetimes. The coordination environment around the metal can be altered synthetically to tune the emission wavelength across the visible spectrum. The synthetic control over the polymer backbone, as well as the iridium(III) ligand environment, allowed us to independently vary each component, which has provided a variety of materials. The materials are characterized through 1H and 13C NMR, mass spectrometry, elemental analysis, electrochemistry, X-Ray diffraction and X-Ray Photoelectron Spectroscopy. The photophysical properties of the materials are studied through UVvii Visible absorption spectroscopy, UV-Vis-NIR spectroelectrochemistry and steadystate/ time-resolved emission spectroscopy. / text

ABSTRACT CHARACTERIZATION OF CONDUCTING POLYMERS OF ESTER LINKAGE CONTAINING THIOPHENE DERIVATIVES VIA MASS SPECTROSCOPY Aslan, Evren M.Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare Co-Supervisor: Prof.Dr. Jale Hacaloglu December 2004, 86 pages In order to investigate the thermal and structural characteristics of terepthalic acid bis-(2-thiophen-3-yl-ethyl)ester (TATE), decanedioic acid bis-(2-thiophen-3-yl- ethyl) ester (DATE) and octanoic acid 2-thiophen-3-yl-ethyl ester (OTE), their corresponding homopolymers, copolymers with thiophene and polythiophene, pyrolysis mass spectrometry technique was utilized. The results were discussed in detail considering the effects of spacer group in between ester linkages. Thermal Gravimetry Analysis was used to investigate the weight loss for polymers and monomers. Conductivities of samples were measured by four-probe technique. It was found that when the ester linkages contain hydrocarbon chains, the growth of polymer occurred through both 2 and 5 positions. On the other hand, when the ester linkages contain more rigid groups such as phenyl, steric hindrance inhibited the growth of the polymer through 2- position and polymerization proceeded via coupling of thiophene moieties mainly at 5-position yielding a polymer with lower conductivity. Though the structure of P(OTE) is inherently different than P(DATE) and P(TATE) extent of network structure is also quite low for this polymer compared to PTh. Similar thermal characterizations were recorded indicating that thermal units were not significantly affected by the presence of TATE, DATE or OTE for all copolymer samples.

Made available in DSpace on 2014-06-11T19:29:06Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-04-13Bitstream added on 2014-06-13T19:38:01Z : No. of bitstreams: 1 cincotto_fh_me_sjrp.pdf: 789637 bytes, checksum: 23f32cf9d8279cacf5618ee5020c1dc6 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A formação de filmes poliméricos contendo azobenzeno tem recebido atenção especial devido à sua aplicação em dispositivos fotônicos. Neste trabalho estudamos a eletropolimerização de Bismarck Brown R (4-3- (2,4-diamin-5-metilfenil)- 4-metilfenildiazenil]diazenil-6-metilbenzeno-1,3-diamindiclorohidrato), filmes ultra-finos sobre substratos de ITO. Foi realizado o estudo do comportamento do filme polimérico variando-se parâmetros durante a etapa de eletropolimerização para a otimização do poliBBR, visando o desenvolvimento de eletrodos modificados para serem utilizados como sensores químicos. O uso da técnica eletroquímica na preparação de filmes poliméricos tem diversas vantagens, tais como a formação do filme diretamente sobre diferentes substratos, controle de espessura do filme, alta reprodutibilidade, geração de polímeros dopados e possibilidade de imobilização de espécies durante a fase de polimerização. Os filmes ultra-finos depositados nos substratos condutores por eletropolimerização foram caracterizados eletroquimicamente (voltametria cíclica e pulso diferencial), espectroscopia de ultravioleta-visível e microscopia de força atômica (AFM). O trabalho se destaca por possuir pouco ou nenhum relato na literatura sobre os dados obtidos dos estudos eletroquímicos e ópticos do comportamento do polímero de Bismarck Brown R. Foram obtidos dados interessantes no comportamento óptico no estudo da imobilização de íons metálicos na estrutura polimérica do BBR, destacando-se as diferentes geometrias e conformações (cis e trans) investigadas no trabalho / The formation of azobenzeno containing polymeric films have been special attention due to its application in photonic devices. In this work we studied the electropolymerization of Bismarck Brown R (4-3-(2,4-diamin-5-methylphenyl)-4-methylphenyldiazenyl]diazenyl-6-methilbenzene-1,3-diamindiclorohidrato), ultra thin films on substrates of ITO. Was carried out study the behavior of the polymer film varying the parameters during the step for the electropolymerization polyBBR optimization, in order to develop modified electrodes to be used as chemical sensors. The use of electrochemical technique for preparing polymer films have several advantages, such as film formation directly on different substrates, film thickness control, high reproducibility, generating doped polymers and possible immobilization of species during the polymerization. The ultra-thin films deposited in conductive substrates were characterized electrochemically (cyclic voltammetry and differential pulse), UV-Vis spectroscopy and atomic force microscopy (AFM). The work stands out due to little or no reports in the literature on data obtained from studies of the electrochemical and optical behavior of polymer Bismarck Brown R. We obtained interesting data on optical behavior in the study immobilization of metal ion in the polymeric structure of the BBR, highlighting the different geometries and conformations (cis and trans) investigated in the work