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Per- and polyfluoroalkyl substances (PFAS) are a group of persistent organic contaminants of which some are toxic and bioaccumulative. Several PFAS can be formed from the atmospheric degradation of precursors such as fluorotelomer alcohols (FTOHs) as well as hydrochlorofluorocarbons (HFCs) and other ozone-depleting chlorofluorocarbon (CFC) replacement compounds. Svalbard ice cores have been shown to provide a valuable record of long-range atmospheric transport of contaminants to the Arctic. This study uses a 12.3 m ice core from the remote Lomonosovfonna ice cap on Svalbard to understand the atmospheric deposition of PFAS in the Arctic. A total of 45 PFAS were targeted, of which 26 were detected, using supercritical fluid chromatography (SFC) tandem mass spectrometry (MS/MS) and ultra-performance liquid chromatography (UPLC) MS/MS. C2 to C11 perfluoroalkyl carboxylic acids (PFCAs) were detected continuously in the ice core and their fluxes ranged from 2.5 to 8200 ng m-2 yr-1 (9.51-16,500 pg L-1). Trifluoroacetic acid (TFA) represented 71 % of the total mass of C2 - C11 PFCAs in the ice core and had increasing temporal trends in deposition. The distribution profile of PFCAs suggested that FTOHs were likely the atmospheric precursor to C8 - C11 PFCAs, whereas C2 - C6 PFCAs had alternative sources, such as HFCs and other CFC replacement compounds. Perfluorooctanesulfonic acid (PFOS) was also widely detected in 82 % of ice core subsections, and its isomer profile (81 % linear) indicated an electrochemical fluorination manufacturing source. Comparisons of PFAS concentrations with a marine aerosol proxy showed that marine aerosols were insignificant for the deposition of PFAS on Lomonosovfonna. Comparisons with a melt proxy showed that TFA and PFOS were mobile during meltwater percolation. This indicates that seasonal snowmelt and runoff from post-industrial accumulation on glaciers could be a significant seasonal source of PFAS to ecosystems in Arctic fjords.

Per- and polyfluoroalkyl substances (PFAS) are a group of persistent organic contaminants of which some are toxic and bioaccumulative. Several PFAS can be formed from the atmospheric degradation of precursors such as fluorotelomer alcohols (FTOHs) as well as hydrochlorofluorocarbons (HFCs) and other ozone-depleting chlorofluorocarbon (CFC) replacement compounds. Svalbard ice cores have been shown to provide a valuable record of long-range atmospheric transport of contaminants to the Arctic. This study uses a 12.3 m ice core from the remote Lomonosovfonna ice cap on Svalbard to understand the atmospheric deposition of PFAS in the Arctic. A total of 45 PFAS were targeted, of which 26 were detected, using supercritical fluid chromatography (SFC) tandem mass spectrometry (MS/MS) and ultra-performance liquid chromatography (UPLC) MS/MS. C2 to C11 perfluoroalkyl carboxylic acids (PFCAs) were detected continuously in the ice core and their fluxes ranged from 2.5 to 8200 ng m-2 yr-1 (9.51-16,500 pg L-1). Trifluoroacetic acid (TFA) represented 71 % of the total mass of C2 - C11 PFCAs in the ice core and had increasing temporal trends in deposition. The distribution profile of PFCAs suggested that FTOHs were likely the atmospheric precursor to C8 - C11 PFCAs, whereas C2 - C6 PFCAs had alternative sources, such as HFCs and other CFC replacement compounds. Perfluorooctanesulfonic acid (PFOS) was also widely detected in 82 % of ice core subsections, and its isomer profile (81 % linear) indicated an electrochemical fluorination manufacturing source. Comparisons of PFAS concentrations with a marine aerosol proxy showed that marine aerosols were insignificant for the deposition of PFAS on Lomonosovfonna. Comparisons with a melt proxy showed that TFA and PFOS were mobile during meltwater percolation. This indicates that seasonal snowmelt and runoff from post-industrial accumulation on glaciers could be a significant seasonal source of PFAS to ecosystems in Arctic fjords., Funding agencies:United Kingdom Research and Innovation Natural Environment Research CouncilOxford Doctoral Training Partnership in Environmental Research NE/L002612/1Burdett-Coutts TrustSvalbard Science Forum Arctic Field Grant 2019 11121Research Council of Norway 196218/S30Fram Centre Flagship program 534/75219

Trifluoroacetic acid (TFA) is a very persistent, very mobile substance (vPvM) with potential toxicity, and causes increasing environmental concerns worldwide. Conventional wastewater treatment strategies are inefficient for selective TFA removal in the presence of inorganic anions. Here we show that surface defunctionalized activated carbon felt (DeACF) carrying anion exchange sites exhibits an outstanding adsorption efficiency towards TFA thanks to introduced electrostatic attraction and enhanced interactions between hydrophobic carbon surface and CF3 moieties (qmax = 30 mg/g, Kd = (840 ± 80) L/kg at cTFA = 3.4 mg/L in tap water). Flow-cell experiments demonstrated a strongly favored TFA uptake by DeACF from tap water over Cl- and SO42- but a remarkable co-adsorption of the inorganic water contaminant NO3-. Electro-assisted TFA desorption using 10 mM Na2SO4 as electrolyte and oxidized ACF as anode showed high recoveries of ≥ 87% at low cell voltages (< 1.1 V). Despite an initial decrease in TFA adsorption capacity (by 33%) caused by partial surface oxidation of DeACF after the 1st ad-/desorption cycle, the system stability was fully maintained over the next 4 cycles. Such electro-assisted ‘trap&release’ approach for TFA removal can be exploited for on-site regenerable adsorption units and as a pre-concentration step combined with degradation technologies.

With the current possible presence of thousands of PFAS compounds in industrial emissions, there is an increasing need to assess the impacts of PFAS regulation of conventional PFAS on one hand and the exposure to emerging and yet unknown PFAS on the other. Today's analytical methodologies using targeted approaches are not sufficient to determine the complete suite of PFAS present. To evaluate the presence of unknown PFAS, we investigated in this study the occurrence of an extended range of target PFAS in various species from the marine and terrestrial Norwegian environment, in relation to the extractable organofluorine (EOF), which yields the total amount of organofluorine. The results showed a varying presence of extractable fluorinated organics, with glaucous gull eggs, otter liver and polar bear plasma showing the highest EOF and a high abundance of PFAS as well. The targeted PFAS measurements explained 1% of the organofluorine for moose liver as the lowest and 94% for otter liver as the highest. PFCAs like trifluoroacetic acid (TFA, reported semi-quantitatively), played a major role in explaining the organic fluorine present. Emerging PFAS as the perfluoroethylcyclohexane sulfonate (PFECHS), was found in polar bear plasma in quantifiable amounts for the first time, confirming earlier detection in arctic species far removed from emission sources. To enable a complete organic fluorine mass balance in wildlife, new approaches are needed, to uncover the presence of new emerging PFAS as cyclic- or ether PFAS together with chlorinated PFAS as well as fluorinated organic pesticides and pharmaceuticals., Funding agencies:Norwegian Environment AgencyNational Research Centre (NRC) 117031

C1-C4 perfluoroalkyl acids (PFAAs) are highly persistent chemicals that have been found in the environment. To date, much uncertainty still exists about their sources and fate. The importance of the atmospheric degradation of volatile precursors to C1-C4 PFAAs were investigated by studying their distribution and seasonal variation in remote Arctic locations. C1-C4 PFAAs were measured in surface snow on the island of Spitsbergen in the Norwegian Arctic during January-August 2019. Trifluoroacetic acid (TFA), perfluoropropanoic acid (PFPrA), perfluorobutanoic acid (PFBA), and trifluoromethane sulfonic acid (TFMS) were detected in most samples, including samples collected at locations presumably receiving PFAA input solely from long-range processes. The flux of TFA, PFPrA, PFBA, and TFMS per precipitation event was in the ranges of 22-1800, 0.79-16, 0.19-170, and 1.5-57 ng/m2, respectively. A positive correlation between the flux of TFA, PFPrA, and PFBA with downward short-wave solar radiation was observed. No correlation was observed between the flux of TFMS and solar radiation. These findings suggest that atmospheric transport of volatile precursors and their subsequent degradation plays a major role in the global distribution of C2-C4 perfluoroalkyl carboxylic acids and their consequential deposition in Arctic environments. The discovery of TFMS in surface snow at these remote Arctic locations suggests that TFMS is globally distributed. However, the transport mechanism to the Arctic environment remains unknown., Funding agencies:British National Environmental Research CouncilOxford Doctoral Training Partnership in Environmental ResearcNE/L002612/1Burdett-Coutts TrustSvalbard Science Forum Arctic Field Grant 2019 11121Research Council of Norway 196218/S30 Fram Centre Flagship program (PharmArctic) 534/75219Knowledge Foundation (Enforce Research Project) 20160019

Ultra-short-chain perfluoroalkyl acids have recently gained attention due to increasing environmental concentrations being observed. The most well-known ultra-short-chain perfluoroalkyl acid is trifluoroacetic acid (TFA) which has been studied since the 1990s. Potential sources and the fate of ultra-short-chain perfluoroalkyl acids other than TFA are not well studied and data reporting their environmental occurrence is scarce. The analytical determination of ultra-short-chain perfluoroalkyl acids is challenging due to their high polarity resulting in low retention using reversed-phase liquid chromatography. Furthermore, recent studies have reported varying extraction recoveries in water samples depending on the water matrix and different methods have been suggested to increase the extraction recovery. The present review gives an overview of the currently used analytical methods and summarizes the findings regarding potential analytical challenges. In addition, the current state of knowledge regarding TFA and other ultra-short-chain perfluoroalkyl acids, namely perfluoropropanoic acid, trifluoromethane sulfonic acid, perfluoroethane sulfonic acid, and perfluoropropane sulfonic acid‚ are reviewed. Both known and potential sources as well as environmental concentrations are summarized and discussed together with their fate and the environmental and human implications., Funding Agency:Örebro University

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young’s modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films.

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young’s modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films.

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young’s modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films.

Reversed-phase liquid chromatography (RPLC) separations of proteins using optical detection generally use trifluoroacetic acid (TFA) because it is a strong, hydrophobic acid and a very effective ion-pairing agent for minimizing chromatographic secondary interactions. Conversely and in order to avoid ion suppression, analyses entailing mass spectrometry (MS) detection is often performed with a weaker ion-pairing modifier, like formic acid (FA), but resolution quality may be reduced. To gain both the chromatographic advantages of TFA and the enhanced MS sensitivity of FA, we explored the use of an alternative acid, difluoroacetic acid (DFA). This acid modifier is less acidic and less hydrophobic than TFA and is believed to advantageously affect the surface tension of electrospray droplets. Thus, it is possible to increase MS sensitivity threefold by replacing TFA with DFA. Moreover, we have observed DFA ion pairing to concomitantly produce higher chromatographic resolution than FA and even TFA. For this reason, we prepared and used MS-quality DFA in place of FA and TFA in separations involving IdeS digested, reduced NIST mAb and a proprietary antibody-drug conjugate (ADC), aiming to increase sensitivity, resolution and protein recovery. The resulting method using DFA was qualified and applied to two other ADCs and gave heightened sensitivity, resolution and protein recovery versus analyses using TFA. This new method, based on a purified, trace metal free DFA, can potentially become a state-of-the-art liquid chromatography-MS technique for the deep characterization of ADCs.

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young’s modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young’s modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young’s modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films.

Reversed-phase liquid chromatography (RPLC) separations of proteins using optical detection generally use trifluoroacetic acid (TFA) because it is a strong, hydrophobic acid and a very effective ion-pairing agent for minimizing chromatographic secondary interactions. Conversely and in order to avoid ion suppression, analyses entailing mass spectrometry (MS) detection is often performed with a weaker ion-pairing modifier, like formic acid (FA), but resolution quality may be reduced. To gain both the chromatographic advantages of TFA and the enhanced MS sensitivity of FA, we explored the use of an alternative acid, difluoroacetic acid (DFA). This acid modifier is less acidic and less hydrophobic than TFA and is believed to advantageously affect the surface tension of electrospray droplets. Thus, it is possible to increase MS sensitivity threefold by replacing TFA with DFA. Moreover, we have observed DFA ion pairing to concomitantly produce higher chromatographic resolution than FA and even TFA. For this reason, we prepared and used MS-quality DFA in place of FA and TFA in separations involving IdeS digested, reduced NIST mAb and a proprietary antibody-drug conjugate (ADC), aiming to increase sensitivity, resolution and protein recovery. The resulting method using DFA was qualified and applied to two other ADCs and gave heightened sensitivity, resolution and protein recovery versus analyses using TFA. This new method, based on a purified, trace metal free DFA, can potentially become a state-of-the-art liquid chromatography-MS technique for the deep characterization of ADCs.

The anodic dissolution of copper electrode in 1 M trifluoroacetic acid (TFA) was investigated by applying linear sweep and cyclic voltammetry. The current-potential (I-E) polarization curves (voltammograms) were interpreted from the perspective of non-linear dynamics. The obtained results showed that the voltammogram can be divided into three separate regions. As the system was moved away from the thermodynamical equilibrium, the first to appear is the region of stable steady-state (marked as SSS1 region). This region was followed by the region of oscillatory states (the OsS region). The SSS1 - GT OsS transition is characterized by bifurcation potential, E (BIF1) = 0.558 V-SCE. The third region, the region of stable steady-state (marked as the SSS2 region) occurs after the OsS - GT SSS2 transition, and is characterized by the potential bifurcation, E (BIF2) = 0.657 V-SCE. The cyclic voltammetry measurement has revealed the lack of hysteresis at the SSS1 a dagger OsS transition, and its existence at the OsS a dagger SSS2 transition (the hysteresis width was 34 mV). The results of this study are presented to demonstrate that the voltammograms of the Cu|1 M TFA oscillating electrochemical system can be considered as a bifurcation diagram, experimentally constructed under dynamical conditions.

The anodic dissolution of copper electrode in 1 M trifluoroacetic acid (TFA) was investigated by applying linear sweep and cyclic voltammetry. The current-potential (I-E) polarization curves (voltammograms) were interpreted from the perspective of non-linear dynamics. The obtained results showed that the voltammogram can be divided into three separate regions. As the system was moved away from the thermodynamical equilibrium, the first to appear is the region of stable steady-state (marked as SSS1 region). This region was followed by the region of oscillatory states (the OsS region). The SSS1 - GT OsS transition is characterized by bifurcation potential, E (BIF1) = 0.558 V-SCE. The third region, the region of stable steady-state (marked as the SSS2 region) occurs after the OsS - GT SSS2 transition, and is characterized by the potential bifurcation, E (BIF2) = 0.657 V-SCE. The cyclic voltammetry measurement has revealed the lack of hysteresis at the SSS1 a dagger OsS transition, and its existence at the OsS a dagger SSS2 transition (the hysteresis width was 34 mV). The results of this study are presented to demonstrate that the voltammograms of the Cu|1 M TFA oscillating electrochemical system can be considered as a bifurcation diagram, experimentally constructed under dynamical conditions.

Polycarbonate-based polymers with a well-defined architecture have become interesting materials due to their large range of applications. Ring opening polymerization (ROP) has been largely applied to make branched polycarbonates. The polymer architectures obtained via this method are strictly related with the polymerization mechanisms involved which depend on the polymerization conditions chosen. Hereby, we evaluate the catalytic activity of three acids, fumaric, trifluoroacetic, and methanesulfonic on the Cationic ROP of trimethylene carbonate (TMC) over a trifunctional initiator, trimethylol propane (TMP), under different reaction conditions. In-detail characterization of the polymers showed the co-existence of two polymerization mechanisms: the activated monomer (AM), which produces a tri-armed branched polycarbonate with inclusion of the TMP initiator (TMP-PTMC), and a combined AM/Activated Chain End (ACE) mechanism, which produces a linear polycarbonate (L-PTMC). Such mixtures were identified for nearly all the reaction variables investigated, together with other side reactions. Upon optimization of the synthesis, the polymerizations in toluene with TFA at 35 °C and equimolar acid/initiator ratio were optimal, avoiding side reactions, but still resulting in a polymer mixture composed of ∼69% TMP-PTMC and 31% of a polycarbonate linear polymer. The occurrence of such mixed polymer architectures is commonly overlooked in literature regarding CROP of branched polycarbonates. We demonstrate the importance of performing a full characterization for a successful detection of polymer mixtures having different (number of) end-functionalities, which are critical for further use in advanced applications, such as in the biomedical or pharmaceutical filed.

Polycarbonate-based polymers with a well-defined architecture have become interesting materials due to their large range of applications. Ring opening polymerization (ROP) has been largely applied to make branched polycarbonates. The polymer architectures obtained via this method are strictly related with the polymerization mechanisms involved which depend on the polymerization conditions chosen. Hereby, we evaluate the catalytic activity of three acids, fumaric, trifluoroacetic, and methanesulfonic on the Cationic ROP of trimethylene carbonate (TMC) over a trifunctional initiator, trimethylol propane (TMP), under different reaction conditions. In-detail characterization of the polymers showed the co-existence of two polymerization mechanisms: the activated monomer (AM), which produces a tri-armed branched polycarbonate with inclusion of the TMP initiator (TMP-PTMC), and a combined AM/Activated Chain End (ACE) mechanism, which produces a linear polycarbonate (L-PTMC). Such mixtures were identified for nearly all the reaction variables investigated, together with other side reactions. Upon optimization of the synthesis, the polymerizations in toluene with TFA at 35 °C and equimolar acid/initiator ratio were optimal, avoiding side reactions, but still resulting in a polymer mixture composed of ∼69% TMP-PTMC and 31% of a polycarbonate linear polymer. The occurrence of such mixed polymer architectures is commonly overlooked in literature regarding CROP of branched polycarbonates. We demonstrate the importance of performing a full characterization for a successful detection of polymer mixtures having different (number of) end-functionalities, which are critical for further use in advanced applications, such as in the biomedical or pharmaceutical filed.

Ova doktorska disertacija se bavi potenciodinamičkim ispitivanjem ponašanja struje pri anodnoj polarizaciji bakarne elektrode, u prisistvu 1M CF3COOH (trifluorosirćetna kiselina). Poseban naglasak je dat na ispitivanje strujnih oscilacija koje se generišu u odreĎenoj oblasti potencijala (oscilatorna oblast, oblast OsS). Pojava strujnih oscilacija ukazuje da se elektrohemijski sistem Cu|1M CF3COOH moţe okarakterisati kao strujni elektrohemijski oscilator. Uočena oscilatorna oblast na struja-potencijal polarizacionim krivama se nalazi izmeĎu dve oblasti stabilnih stacionarnih stanja, naime izmeĎu oblasti aktivnog rastvaranja bakarne elektrode (oblast SSS1) i oblasti njene pasivacije (oblast SSS2). Primenom ciklične voltametrije ustanovljeno je da se strujne oscilacije javljaju pri oba smera polarizacije, anodnom i katodnom smeru. Prelaz SSS1OsS karakteriše zanemarljivo mali histerezis (5 mV), dok je širina histerezisa na prelazu OsSSSS2 značajno veća (34 mV). Bifurkaciona analiza je pokazala da se prelaz SSS1OsS odvija preko superkritične Hopfove bifurkacije, dok je prelaz OsSSSS2 okarakterisan homokliničnom bifurkacijom. Tafelova analiza je pokazala da se anodno rastvaranje bakarne elektrode odvija preko mehanizma jednoelektronskog prenosa naelektrisanja. Rendgeno-difrakcionom analizom ustanovljeno je da oksidi bakra (CuO i Cu2O) ne ulaze u sastav pasivnog sloja. Difrakciona refleksija na 2 = 7,95, koja nije mogla biti indeksirana, ulazuje da se u sastavu pasivnog sloja nalazi faza velike elementarne ćelije, najverovatnije so koju čine Cu(I) i/ili Cu(II) trifluoroacetat. Dobijena mikro-porozna struktura površine bakarne elektrode koja je bila izloţena potencijalima unutar oscilatorne oblasti je detektovana primenom mikroskopije atomskih sila, što ukazuje na tačkastu (piting) koroziju. Na osnovu ispitivanja uticaja temperature elektrolitičke ćelije na oscilatorno ponašanje struje, naĎeno je da se unutar temperaturskog intervala 5 – 52 C strujne oscilacije javlj, This doctoral dissertation deals with potentiodynamic examination of current response during the anodic polarization of copper electrode in the presence of 1M CF3COOH (trifluoroacetic acid). Particular focus is given on investigation of the current oscillations that are generated in certain potential region (oscillatory region, region OsS). Appearance of the current oscillations indicates that the electrochemical system Cu|1M CF3COOH can be classified as a current electrochemical oscillator. The observed oscillatory region at the current-potential polarization curve is situated between two regions of stable steady states, namely between the region of active dissolution of copper electrode (region SSS1) and the region of its passivation (region SSS2). It was determined that the current oscillations occur in anodic and cathodic direction of polarization, by applying of cyclic voltammetry. The transition SSS1OsS is characterized by negligible hysteresis (5 mV), while the width of hysteresis at the transition OsSSSS2 is significantly higher (34 mV). Bifurcation analysis showed that the transition SSS1OsS goes via supercritical Hopf bifurcation, while the transition OsSSSS2 is characterize by homoclinic bifurcation. The Tafel analysis showed that the anodic dissolution of copper electrode immersed in 1M CF3COOH goes via one-electron charge transfer step. X-ray diffraction analysis showed absence of copper oxides (Cu2O and CuO) in passive layer. Diffraction reflections at 2 = 7.95, which could not be indexed, indicates presence of phase with large unit cell in passive layer, most probably salt composed of Cu(I) or/and Cu(II) trifluoroacetate. Obtained micro-porous structure of the copper electrode surface, which was exposed to potentials within oscillatory region was detected by using atomic force microscopy, this indicates a pitting corrosion. Based on the investigation of the temperature effect on current oscillatory behavior, it was found that within temperature

Ova doktorska disertacija se bavi potenciodinamičkim ispitivanjem ponašanja struje pri anodnoj polarizaciji bakarne elektrode, u prisistvu 1M CF3COOH (trifluorosirćetna kiselina). Poseban naglasak je dat na ispitivanje strujnih oscilacija koje se generišu u odreĎenoj oblasti potencijala (oscilatorna oblast, oblast OsS). Pojava strujnih oscilacija ukazuje da se elektrohemijski sistem Cu|1M CF3COOH moţe okarakterisati kao strujni elektrohemijski oscilator. Uočena oscilatorna oblast na struja-potencijal polarizacionim krivama se nalazi izmeĎu dve oblasti stabilnih stacionarnih stanja, naime izmeĎu oblasti aktivnog rastvaranja bakarne elektrode (oblast SSS1) i oblasti njene pasivacije (oblast SSS2).Primenom ciklične voltametrije ustanovljeno je da se strujne oscilacije javljaju pri oba smera polarizacije, anodnom i katodnom smeru. Prelaz SSS1OsS karakteriše zanemarljivo mali histerezis (5 mV), dok je širina histerezisa na prelazu OsSSSS2 značajno veća (34 mV). Bifurkaciona analiza je pokazala da se prelaz SSS1OsS odvija preko superkritične Hopfove bifurkacije, dok je prelaz OsSSSS2 okarakterisan homokliničnom bifurkacijom.Tafelova analiza je pokazala da se anodno rastvaranje bakarne elektrode odvija preko mehanizma jednoelektronskog prenosa naelektrisanja. Rendgeno-difrakcionom analizom ustanovljeno je da oksidi bakra (CuO i Cu2O) ne ulaze u sastav pasivnog sloja. Difrakciona refleksija na 2 = 7,95, koja nije mogla biti indeksirana, ulazuje da se u sastavu pasivnog sloja nalazi faza velike elementarne ćelije, najverovatnije so koju čine Cu(I) i/ili Cu(II) trifluoroacetat. Dobijena mikro-porozna struktura površine bakarne elektrode koja je bila izloţena potencijalima unutar oscilatorne oblasti je detektovana primenom mikroskopije atomskih sila, što ukazuje na tačkastu (piting) koroziju.Na osnovu ispitivanja uticaja temperature elektrolitičke ćelije na oscilatorno ponašanje struje, naĎeno je da se unutar temperaturskog intervala 5 – 52 C strujne oscilacije javljaju, This doctoral dissertation deals with potentiodynamic examination of current response during the anodic polarization of copper electrode in the presence of 1M CF3COOH (trifluoroacetic acid). Particular focus is given on investigation of the current oscillations that are generated in certain potential region (oscillatory region, region OsS). Appearance of the current oscillations indicates that the electrochemical system Cu|1M CF3COOH can be classified as a current electrochemical oscillator. The observed oscillatory region at the current-potential polarization curve is situated between two regions of stable steady states, namely between the region of active dissolution of copper electrode (region SSS1) and the region of its passivation (region SSS2).It was determined that the current oscillations occur in anodic and cathodic direction of polarization, by applying of cyclic voltammetry. The transition SSS1OsS is characterized by negligible hysteresis (5 mV), while the width of hysteresis at the transition OsSSSS2 is significantly higher (34 mV). Bifurcation analysis showed that the transition SSS1OsS goes via supercritical Hopf bifurcation, while the transition OsSSSS2 is characterize by homoclinic bifurcation.The Tafel analysis showed that the anodic dissolution of copper electrode immersed in 1M CF3COOH goes via one-electron charge transfer step. X-ray diffraction analysis showed absence of copper oxides (Cu2O and CuO) in passive layer. Diffraction reflections at 2 = 7.95, which could not be indexed, indicates presence of phase with large unit cell in passive layer, most probably salt composed of Cu(I) or/and Cu(II) trifluoroacetate. Obtained micro-porous structure of the copper electrode surface, which was exposed to potentials within oscillatory region was detected by using atomic force microscopy, this indicates a pitting corrosion.Based on the investigation of the temperature effect on current oscillatory behavior, it was found that within temperature int

Boron tris(trifluoroacetate) is identified as the first effective catalyst for the homoallyl- and homocrotylboration of aldehydes by cyclopropylcarbinylboronates. NMR spectroscopic studies and theoretical calculations of key intermediates and transition states both suggest that a ligand-exchange mechanism, akin to our previously reported PhBCl2-promoted homoallylations, is operative. Our experimental and theoretical results also suggest that the catalytic activity of boron tris(trifluoroacetate) might originate from more facile catalytic turnover of the trifluoroacetate ligands (in agreement with DFT calculations) or from a lower propensity for formation of off-pathway reservoir intermediates (as observed by (1)H NMR). This work shows that carboxylates are viable catalytic ligands for homoallyl- and homocrotylations of carbonyl compounds and opens the door to the development of catalytic asymmetric versions of this transformation.

Boron tris(trifluoroacetate) is identified as the first effective catalyst for the homoallyl- and homocrotylboration of aldehydes by cyclopropylcarbinylboronates. NMR spectroscopic studies and theoretical calculations of key intermediates and transition states both suggest that a ligand-exchange mechanism, akin to our previously reported PhBCl2-promoted homoallylations, is operative. Our experimental and theoretical results also suggest that the catalytic activity of boron tris(trifluoroacetate) might originate from more facile catalytic turnover of the trifluoroacetate ligands (in agreement with DFT calculations) or from a lower propensity for formation of off-pathway reservoir intermediates (as observed by (1)H NMR). This work shows that carboxylates are viable catalytic ligands for homoallyl- and homocrotylations of carbonyl compounds and opens the door to the development of catalytic asymmetric versions of this transformation.

Trifluoroacetic acid (TFA) was found as an efficient catalyst for the synthesis of amidoalkyl naphthols from aromatic aldehydes, β-naphthol and acetamide/benzamide under solvent free condition at 80o C. All the synthesized compounds were characterized by IR, 1H NMR and Mass spectra. The advantages of the new method were good yields, short reaction times, simple work-up, inexpensive and easily available catalyst and economical due to absence of solvent. Therefore, this method could be an attractive alternative to existing methods for the synthesis of biologically important amidoalkyl naphthols.

The reference measurement procedure for determination of HbA1c (glycated haemoglobin) using HPLC(high performance liquid chromatography)-ESI(electrospray ionisation)-MS(mass spectrometry) has been modified. Main modifications were a change in the buffer composition of the HPLC, a change in the gradient elution profile and the introduction of a post-column splitting system. The long-term stability of the HPLC-ESI-MS system proved to be of high importance to get reproducible results. Using the modified HPLC conditions stable retention times, high peak symmetry and a good column batch-to-batch reproducibility of the analytical results were obtained.The mean deviation from the target values was less than 0.7% with an imprecision of less than 2%., Das Referenzmessverfahren zur Bestimmung von HbA1c (glykiertes Hämoglobin) mittels HPLC(Hochleistungsflüssigkeitschromatografie)-ESI(Elektrospray-Ionisation)-MS(Massenspektrometrie) wurde modifiziert. Die wesentlichen Modifikationen bestehen in der Änderung der Zusammensetzung des HPLC-Puffers, der Änderung des Gradientenelutionsprofils und der Einführung eines "post-column splitting" Systems. Darüber hinaus erwies sich die Langzeitstabilität des HPLC-ESI-MS Systems als äußerst wichtig für die Reproduzierbarkeit der Ergebnisse. Unter Verwendung der modifizierten HPLC Bedingungen wurden stabile Retentionszeiten, eine hohe Peaksymmetrie und eine gute Reproduzierbarkeit, auch bei verschiedenen Säulenchargen erreicht. Es wurde eine Abweichung von den Zielwerten von weniger als 0,7% und eine Unpräzision von weniger als 2% erzielt.

This Article is from 'Peptides, Chemistry and Biology: Proceedings of the American Peptide Symposium (12th) Held in Cambridge, Massachusetts on 16-21 June 1991', AD-A256 113, p613-614.

Excreted amount of urinary trifluoroacetic acid (TFA) during and after halothane anesthesia in twelve surgical patients was determined isotachophoretically. The levels of urinary TFA which amount was zero or a trace during the anesthesia increased after discontinuation of halothane inhalation. The values of daily excreted TFA were the highest on the 2.1±0.3 postoperative day (M±SEM). The urinary TFA values of patients inhaling a low concentration (0.8%) of halothane reverted to zero or a trace level on the 11.2±1.0 postoperative day (M±SEM) and the total amount of averaged 21.53 ± 3.23 mmol (M ± SEM). In patients to levels seen on the 7 .0 ± 0.6 postoperative day (M±SEM) and the total amount of TFA excreted was 20.20±4.77 mmol (M±SEM). These clinical findings indicate that the aerobic biotransformation of halothane after anesthesia is enhanced by high concentration of halothane., Supported in part by Research Grants No.57480297 and 57570564 from the Ministry of Education, Science and Culture, Japan. Presented in part at the 7th World Congress of Anesthesiologists, Hamburg, September 1980.

Excreted amount of urinary trifluoroacetic acid (TFA) during and after halothane anesthesia in twelve surgical patients was determined isotachophoretically. The levels of urinary TFA which amount was zero or a trace during the anesthesia increased after discontinuation of halothane inhalation. The values of daily excreted TFA were the highest on the 2.1±0.3 postoperative day (M±SEM). The urinary TFA values of patients inhaling a low concentration (0.8%) of halothane reverted to zero or a trace level on the 11.2±1.0 postoperative day (M±SEM) and the total amount of averaged 21.53 ± 3.23 mmol (M ± SEM). In patients to levels seen on the 7 .0 ± 0.6 postoperative day (M±SEM) and the total amount of TFA excreted was 20.20±4.77 mmol (M±SEM). These clinical findings indicate that the aerobic biotransformation of halothane after anesthesia is enhanced by high concentration of halothane., Supported in part by Research Grants No.57480297 and 57570564 from the Ministry of Education, Science and Culture, Japan. Presented in part at the 7th World Congress of Anesthesiologists, Hamburg, September 1980.

type:text, Excreted amount of urinary trifluoroacetic acid (TFA) during and after halothane anesthesia in twelve surgical patients was determined isotachophoretically. The levels of urinary TFA which amount was zero or a trace during the anesthesia increased after discontinuation of halothane inhalation. The values of daily excreted TFA were the highest on the 2.1±0.3 postoperative day (M±SEM). The urinary TFA values of patients inhaling a low concentration (0.8%) of halothane reverted to zero or a trace level on the 11.2±1.0 postoperative day (M±SEM) and the total amount of averaged 21.53 ± 3.23 mmol (M ± SEM). In patients to levels seen on the 7 .0 ± 0.6 postoperative day (M±SEM) and the total amount of TFA excreted was 20.20±4.77 mmol (M±SEM). These clinical findings indicate that the aerobic biotransformation of halothane after anesthesia is enhanced by high concentration of halothane., Supported in part by Research Grants No.57480297 and 57570564 from the Ministry of Education, Science and Culture, Japan. Presented in part at the 7th World Congress of Anesthesiologists, Hamburg, September 1980.

The optimal composition of eluant for trifluoroacetic acid (TFAA) analysis by ion-exchange chromatography was determined and a preliminary study to detect TFAA, a metabolite of isoflurane, in bile of rabbits during and after inhalation of isoflurane was made. The optimal composition of eluant for TFAA analysis by ion-exchange chromatography was determined to be a solution of 2rnM Na2C03 and 4mM NaHC03. Rabbits were divided into 4 groups; A group: 1 hr inhalation of 2% isoflurane, B group: 2 hr inhalation of 2% isoflurane, C group: 2 hr inhalation of 3% isoflurane, and D group: 2 hr inhalation of 4% isoflurane. The maximum biliary TFAA concentration in groups A, B, C and D averaged 17.5 ± 1.4 μM (mean ± S.D.) at 105 min, 37.1 ± 11.5 μM at 315 min, 54.5 ± 9.4 μM at 585 min and 34.4 ± 12.1 μM at 555 min after termination of inhalation. Cumulative excreted amounts of biliary TFAA for 20 hours were 746 nmols in A group (8 hours), 3,421 mnols in B group, 6,582 nmols in C group and 3,267 nmols in D group. Half-lives of biliary excreted TFAA were 63 min, 325 min, 478 min and 546 min, respectively. These results showed that ion-exchange chromatography is more convenient for detecting TFAA as a metabolite of isoflurane than isotachophoresis, gas chromatography, paper chromatography and thin layer chromatography and that TFAA was determined as a biliary metabolite of isoflurane in the rabbit.

Research results are contained in the publications listed below: Synthesis and Some Reactions of Hexaazatriphenylene Hexanitrile, a Hydrogen-Free Polyfunctional Heterocycle with D3h Symmetry, Decarboxylative Synthesis of Hexaazatriphenylene, Nitrosations in Anhydrous Trifluoroacetic Acid Media: A modification for Insoluble or Deactivated Amine and Amide Precursors, Materials Derived from the Hydrogen-Free Heterocycle Hexaazatriphenylene Hexacarbonitrile Syntheses and High Temperature Properties of Polyimides, A Highly Crosslinked, Thermally Stable Polyimide Film Derived From Hexaazatriphenylene, Syntheses of Some Hexacarboxylic Acid Derivatives of Hexaazatriphenylene, Synthesis and Thermogravimetric Analyses of Trisimides and Polyimides Derived from Hexaazatriphenylene.

Heating 1-vinyl-4,5,6,7-tetrahydro-5-methyl-4,6-ethanopyrrolo[3,2-c]pyridme (1) in the presence of acetic or trifluoroacetic anhydride resulted in bicyclic saturated fragment cleavage, affording cyclohepteno[b]pyrroles 2a,b in low yields. In the case of trifluoroacetic anhydride, the major product of the reaction, -trifluoroacetylsubstituted tetrahydropyrrolo[3,2-c]pyridine 3 was isolated in 34% yield.

Excreted amount of urinary trifluoroacetic acid (TFA) during and after halothane anesthesia in twelve surgical patients was determined isotachophoretically. The levels of urinary TFA which amount was zero or a trace during the anesthesia increased after discontinuation of halothane inhalation. The values of daily excreted TFA were the highest on the 2.1±0.3 postoperative day (M±SEM). The urinary TFA values of patients inhaling a low concentration (0.8%) of halothane reverted to zero or a trace level on the 11.2±1.0 postoperative day (M±SEM) and the total amount of averaged 21.53 ± 3.23 mmol (M ± SEM). In patients to levels seen on the 7 .0 ± 0.6 postoperative day (M±SEM) and the total amount of TFA excreted was 20.20±4.77 mmol (M±SEM). These clinical findings indicate that the aerobic biotransformation of halothane after anesthesia is enhanced by high concentration of halothane., Supported in part by Research Grants No.57480297 and 57570564 from the Ministry of Education, Science and Culture, Japan. Presented in part at the 7th World Congress of Anesthesiologists, Hamburg, September 1980.