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The pressure dependence of sheath gas assisted electrospray ionization (ESI) was investigated based on two complementary experimental setups, namely an ESI-ion mobility (IM) spectrometer and an ESI capillary - Faraday plate setup housed in an optically accessible vacuum chamber. The ESI-IM spectrometer is capable of working in the pressure range between 300 and 1000 mbar. Another aim was the assessment of the analytical capabilities of a subambient pressure ESI-IM spectrometer. The pressure dependence of ESI was characterized by imaging the electrospray and recording current-voltage (I-U) curves. Qualitatively different behavior was observed in both setups. While the current rises continuously with the voltage in the capillary-plate setup, a sharp increase of the current was measured in the IM spectrometer above a pressure-dependent threshold voltage. The different character can be attributed to the detection of different species in both experiments. In the capillary-plate experiment, a multitude of charged species are detected while only desolvated ions attribute to the IM spectrometer signal. This finding demonstrates the utility of IM spectrometry for the characterization of ESI, since in contrast to the capillary-plate setup, the release of ions from the electrospray droplets can be observed. The I-U curves change significantly with pressure. An important result is the reduction of the maximum current with decreasing pressure. The connected loss of ionization efficiency can be compensated by a more efficient transfer of ions in the IM spectrometer at increased E/N. Thus, similar limits of detection could be obtained at 500 mbar and 1 bar.
The capability of electrospray ionization (ESI)-ion mobility (IM) spectrometry for reaction monitoring is assessed both as a stand-alone real-time technique and in combination with HPLC. A three-step chemical reaction, consisting of a Williamson ether synthesis followed by a hydrogenation and an N-alkylation step, is chosen for demonstration. Intermediates and products are determined with a drift time to mass-per-charge correlation. Addition of an HPLC column to the setup increases the separation power and allows the determination of further species. Monitoring of the intensities of the various species over the reaction time allows the detection of the end of reaction, determination of the rate-limiting step, observation of the system response in discontinuous processes, and optimization of the mass ratios of the starting materials. However, charge competition in ESI influences the quantitative detection of substances in the reaction mixture. Therefore, two different methods are investigated, which allow the quantification and investigation of reaction kinetics. The first method is based on the pre-separation of the compounds on an HPLC column and their subsequent individual detection in the ESI-IM spectrometer. The second method involves an extended calibration procedure, which considers charge competition effects and facilitates nearly real-time quantification.
Die Elektrosprayionisation (ESI) ist eine der weitverbreitetsten Ionisationstechniken für flüssige Pro-ben in der Massen- und Ionenmobilitäts(IM)-Spektrometrie. Aufgrund ihrer schonenden Ionisierung wird ESI vorwiegend für empfindliche, komplexe Moleküle in der Biologie und Medizin eingesetzt. Überdies ist sie allerdings für ein sehr breites Spektrum an Substanzklassen anwendbar. Die IM-Spektrometrie wurde ursprünglich zur Detektion gasförmiger Proben entwickelt, die hauptsächlich durch radioaktive Quellen ionisiert werden. Sie ist die einzige analytische Methode, bei der Isomere in Echtzeit getrennt und über ihre charakteristische IM direkt identifiziert werden können. ESI wurde in den 90ger Jahren durch die Hill Gruppe in die IM-Spektrometrie eingeführt. Die Kombination wird bisher jedoch nur von wenigen Gruppen verwendet und hat deshalb noch ein hohes Entwick-lungspotential. Ein vielversprechendes Anwendungsfeld ist der Einsatz in der Hochleistungs-flüssigkeitschromatographie (HPLC) zur mehrdimensionalen Trennung. Heutzutage ist die HPLC die Standardmethode zur Trennung komplexer Proben in der Routineanalytik. HPLC-Trennungsgänge sind jedoch häufig langwierig und der Einsatz verschiedener Laufmittel, hoher Flussraten, von Puffern, sowie Laufmittelgradienten stellt hohe Anforderungen an die Detektoren. Die ESI-IM-Spektrometrie wurde in einigen Studien bereits als HPLC-Detektor eingesetzt, war dort bisher jedoch auf Flussratensplitting oder geringe Flussraten des Laufmittels beschränkt.
In dieser kumulativen Doktorarbeit konnte daher erstmals ein ESI IM-Spektrometer als HPLC-Detektor für den Flussratenbereich von 200-1500 μl/min entwickelt werden. Anhand von fünf Publi-kationen wurden (1) über eine umfassende Charakterisierung die Eignung des Spektrometers als HPLC-Detektor festgestellt, (2) ausgewählte komplexe Trenngänge präsentiert und (3) die Anwen-dung zum Reaktionsmonitoring und (4, 5) mögliche Weiterentwicklungen gezeigt.
Erfolgreich konnten mit dem selbst-entwickelten ESI IM-Spektrometer typische HPLC-Bedingungen wie Wassergehalte im Laufmittel von bis zu 90%, Pufferkonzentrationen von bis zu 10 mM, sowie Nachweisgrenzen von bis zu 50 nM erreicht werden. Weiterhin wurde anhand der komplexen Trennungsgänge (24 Pestizide/18 Aminosäuren) gezeigt, dass die HPLC und die IM-Spektrometrie eine hohe Orthogonalität besitzen. Eine effektive Peakkapazität von 240 wurde so realisiert. Auf der HPLC-Säule koeluierende Substanzen konnten über die Driftzeit getrennt und über ihre IM identifi-ziert werden, sodass die Gesamttrennzeiten erheblich minimiert werden konnten. Die Anwend-barkeit des ESI IM-Spektrometers zur Überwachung chemischer Synthesen wurde anhand einer dreistufigen Reaktion demonstriert. Es konnten die wichtigsten Edukte, Zwischenprodukte und Produkte aller Stufen identifiziert werden. Eine quantitative Auswertung war sowohl über eine kurze HPLC-Vortrennung als auch durch die Entwicklung eines eigenen Kalibrierverfahrens, welches die Ladungskonkurrenz bei ESI berücksichtigt, ohne HPLC möglich. Im zweiten Teil der Arbeit werden zwei Weiterentwicklungen des Spektrometers präsentiert. Eine Möglichkeit ist die Reduzierung des Drucks in den intermediären Bereich (300 - 1000 mbar) mit dem Ziel der Verringerung der benötigten Spannungen. Mithilfe von Streulichtbildern und Strom-Spannungs-Kurven wurden für geringe Drücke eine verminderte Freisetzung der Analyt-Ionen aus den Tropfen festgestellt. Die Verluste konnten jedoch über höhere elektrische Feldstärken ausgeglichen werden, sodass gleiche Nachweisgrenzen bei 500 mbar und bei 1 bar erreicht wurden. Die zweite Weiterentwicklung ist ein neuartiges Ionentors mit Pulsschaltung, welches eine Verdopplung der Auflösung auf bis zu R > 100 bei gleicher Sensitivität ermöglichte. Eine denkbare Anwendung im Bereich der Peptidanalytik wurde mit beachtlichen Auflösungen der Peptide von R = 90 gezeigt.
The isothermal vacuum-induced dehydration of thin films made of poly(methoxy diethylene glycol acrylate) (PMDEGA), which were swollen under ambient conditions, is studied. The dehydration behavior of the homopolymer film as well as of a nanostructured film of the amphiphilic triblock copolymer polystyrene-block-poly(methoxy diethylene glycol acrylate)-block-polystyrene, abbreviated as PS-b-PMDEGA-b-PS, are probed, and compared to the thermally induced dehydration behavior of such thin thermo-responsive films when they pass through their LCST-type coil-to globule collapse transition. The dehydration kinetics is followed by in-situ neutron reflectivity measurements. Contrast results from the use of deuterated water. Water content and film thickness are significantly reduced during the process, which can be explained by Schott second order kinetics theory for both films. The water content of the dehydrated equilibrium state from this model is very close to the residual water content obtained from the final static measurements, indicating that residual water still remains in the film even after prolonged exposure to the vacuum. In the PS-b-PMDEGA-b-PS film that shows micro-phase separation, the hydrophobic PS domains modify the dehydration process by hindering the water removal, and thus retarding dehydration by about 30%. Whereas residual water remains tightly bound in the PMDEGA domains, water is completely removed from the PS domains of the block copolymer film. (C) 2017 Elsevier Ltd. All rights reserved.
4-Methyl-1-vinyl-1,2,4-triazolium triiodide ionic liquid and its polymer poly(4-methyl-1-vinyl-1,2,4-triazolium) triiodide were prepared for the first time from their iodide precursors via the reaction of iodide (I-) with elemental iodine (I-2). The change from iodide to triiodide (I-3(-)) was found to introduce particular variations in the physical properties of these two compounds, including lower melting point/glass transition temperature and altered solubility. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, and their electrochemical properties examined in solution and in the solid-state. Compared with their iodide analogues, the triiodide salts exhibited lower electrical impedance and higher current in the cyclic voltammetry. We found that poly(4-methyl-1,2,4-triazolium triiodide) was proven to be a promising solid polymer electrolyte candidate. (C) 2017 Elsevier Ltd. All rights reserved.
2-Deoxy-D-ribose-5-phosphate aldolase (DERA) is a biocatalyst that is capable of converting acetaldehyde and a second aldehyde as acceptor into enantiomerically pure mono- and diyhydroxyaldehydes, which are important structural motifs in a number of pharmaceutically active compounds. However, substrate as well as product inhibition requires a more-sophisticated process design for the synthesis of these motifs. One way to do so is to the couple aldehyde conversion with transport processes, which, in turn, would require an immobilization of the enzyme within a thin film that can be deposited on a membrane support. Consequently, we developed a fabrication process for such films that is based on the formation of DERA-poly(N-isopropylacrylamide) conjugates that are subsequently allowed to self-assemble at an air-water interface to yield the respective film. In this contribution, we discuss the conjugation conditions, investigate the interfacial properties of the conjugates, and, finally, demonstrate a successful film formation under the preservation of enzymatic activity.
Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.
N-terminal methacrylation of peptide MAXI, which is capable of conformational changes variation of the pH, results in a peptide, named VK20. Increasing the reactivity of this terminal group enables further coupling reactions or chemical modifications of the peptidc. However, this end group functionalization may influence the ability of confonnational changes of VK20; as well as its properties. In this paper; the influence of pH on the transition between random coil and beta-sheet conformation of VK20; including the transition kinetics, were investigated. At pH values of 9 and higher, the kinetics beta-sheet formation increased tor VK(2 0, compared to MAXI. The self-assembly into beta-sheets recognized by the formation of a physically crosslinked gel was furthermore indicated by a significant increase of G. An increase in pH (from 9 to 9.5) led to a faster gelation of the peptide VK20. Simultaneously, G was increased from 460 +/- 70 Pa (at pH 9) to 1520 +/- 180 Pa (at pH 9.5). At the nanoscale, the gel showed a highly interconnected fibrillar/network structure with uniform fibril widths of approximately 3.4 +/- 0.5 nm (N=30). The recovery of the peptide conformation back to random coil resulted in the dissolution of the gel; whereby the kinetics of the recovery depended on the pH. Conclusively, the ability of MAXI to undergo confommtional changes was not affected by N-terminal methacrylation whereas the kinetics of pH-sensitive beta-sheet formations has been increased.
Conformational transition of peptide-functionalized cryogels enabling shape-memory capability
(2017)
In nature, proteins self-assemble into various structures with different dimensions. To construct these nanostructures in laboratories, normally proteins with different symmetries are selected. However, most of these approaches are engineering-intensive and highly dependent on the accuracy of the protein design. Herein, we report that a simple native protein LecA assembles into one-dimensional nanoribbons and nanowires, two-dimensional nanosheets, and three-dimensional layered structures controlled mainly by small-molecule assembly-inducing ligands RnG (n = 1, 2, 3, 4, 5) with varying numbers of ethylene oxide repeating units. To understand the formation mechanism of the different morphologies controlled by the small-molecule structure, molecular simulations were performed from microscopic and mesoscopic view, which presented a clear relationship between the molecular structure of the ligands and the assembled patterns. These results introduce an easy strategy to control the assembly structure and dimension, which could shed light on controlled protein assembly.
Degradable multiblock copolymers prepared from equal weight amounts of poly(epsilon-caprolactone)-diol (PCL-diol) and poly[oligo(3S-iso-butylmorpholine-2,5-dione)]-diol (PIBMD-diol), named PCL-PIBMD, provide a phase-segregated morphology. It exhibits a low melting temperature from PCL domains (T-m,T-PCL) of 382 degrees C and a high T-m,T-PIBMD of 170 +/- 2 degrees C with a glass transition temperature (T-g,T-PIBMD) at 42 +/- 2 degrees C from PIBMD domains. In this study, we explored the influence of applying different thermal treatments on the resulting morphologies of solution-cast and spin-coated PCL-PIBMD thin films, which showed different initial surface morphologies. Differential scanning calorimetry results and atomic force microscopy images after different thermal treatments indicated that PCL and PIBMD domains showed similar crystallization behaviors in 270 +/- 30 mu m thick solution-cast films as well as in 30 +/- 2 and 8 +/- 1nm thick spin-coated PCL-PIBMD films. Existing PIBMD crystalline domains highly restricted the generation of PCL crystalline domains during cooling when the sample was annealed at 180 degrees C. By annealing the sample above 120 degrees C, the PIBMD domains crystallized sufficiently and covered the free surface, which restricted the crystallization of PCL domains during cooling. The PCL domains can crystallize by hindering the crystallization of PIBMD domains via the fast vitrification of PIBMD domains when the sample was cooled/quenched in liquid nitrogen after annealing at 180 degrees C. These findings contribute to a better fundamental understanding of the crystallization mechanism of multi-block copolymers containing two crystallizable domains whereby the T-g of the higher melting domain type is in the same temperature range as the T-m of the lower melting domain type. Copyright (c) 2016 John Wiley & Sons, Ltd.
This work presents a fabrication of thermoresponsive plasmonic core-satellite nanoassemblies. The structure has a silica nanoparticle core surrounded by gold nanoparticle satellites using thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) chains as scaffolds. The thiol-terminated PNIPAM shell is densely grafted on the silica core via surface-initiated reversible addition-fragmentation chain transfer polymerization and used to anchor numerous gold nanoparticle satellites with a tunable stoichiometry. Below and above lower critical solution temperature, the chain conformation of PNIPAM reversibly changes between swollen and shrunken state. The reversible change of the polymer size varies the refractive index of the local medium surrounding the satellites and the distance between them. The two effects together lead to the thermoresponsive plasmonic properties of the nanoassemblies. Under different satellite densities, two distinctive plasmonic features appear.
Molecules often fragment after photoionization in the gas phase. Usually, this process can only be investigated spectroscopically as long as there exists electron correlation between the photofragments. Important parameters, like their kinetic energy after separation, cannot be investigated. We are reporting on a femtosecond time-resolved Auger electron spectroscopy study concerning the photofragmentation dynamics of thymine. We observe the appearance of clearly distinguishable signatures from thymines neutral photofragment isocyanic acid. Furthermore, we observe a time-dependent shift of its spectrum, which we can attribute to the influence of the charged fragment on the Auger electron. This allows us to map our time-dependent dataset onto the fragmentation coordinate. The time dependence of the shift supports efficient transformation of the excess energy gained from photoionization into kinetic energy of the fragments. Our method is broadly applicable to the investigation of photofragmentation processes.
The motivation of this work was to investigate the self-assembly of a block copolymer species that attended little attraction before, double hydrophilic block copolymers (DHBCs). DHBCs consist of two linear hydrophilic polymer blocks. The self-assembly of DHBCs towards suprastructures such as particles and vesicles is determined via a strong difference in hydrophilicity between the corresponding blocks leading to a microphase separation due to immiscibility. The benefits of DHBCs and the corresponding particles and vesicles, such as biocompatibility, high permeability towards water and hydrophilic compounds as well as the large amount of possible functionalizations that can be addressed to the block copolymers make the application of DHBC based structures a viable choice in biomedicine. In order to assess a route towards self-assembled structures from DHBCs that display the potential to act as cargos for future applications, several block copolymers containing two hydrophilic polymer blocks were synthesized. Poly(ethylene oxide)-b-poly(N-vinylpyrrolidone) (PEO-b-PVP) and Poly(ethylene oxide)-b-poly(N-vinylpyrrolidone-co-N-vinylimidazole) (PEO-b-P(VP-co-VIm) block copolymers were synthesized via reversible deactivation radical polymerization (RDRP) techniques starting from a PEO-macro chain transfer agent. The block copolymers displayed a concentration dependent self-assembly behavior in water which was determined via dynamic light scattering (DLS). It was possible to observe spherical particles via laser scanning confocal microscopy (LSCM) and cryogenic scanning electron microscopy (cryo SEM) at highly concentrated solutions of PEO-b-PVP. Furthermore, a crosslinking strategy with (PEO-b-P(VP-co-VIm) was developed applying a diiodo derived crosslinker diethylene glycol bis(2-iodoethyl) ether to form quaternary amines at the VIm units. The formed crosslinked structures proved stability upon dilution and transfer into organic solvents. Moreover, self-assembly and crosslinking in DMF proved to be more advantageous and the crosslinked structures could be successfully transferred to aqueous solution. The afforded spherical submicron particles could be visualized via LSCM, cryo SEM and Cryo TEM.
Double hydrophilic pullulan-b-poly(acrylamide) block copolymers were synthesized via copper catalyzed alkyne azide cycloaddition (CuAAC) starting from suitable pullulan alkyne and azide functionalized poly(N,N-dimethylacrylamide) (PDMA) and poly(N-ethylacrylamide) (PEA) homopolymers. The conjugation reaction was confirmed via SEC and 1H-NMR measurements. The self-assembly of the block copolymers was monitored with DLS and static light scattering (SLS) measurements indicating the presence of hollow spherical structures. Cryo SEM measurements could confirm the presence of vesicular structures for Pull-b-PEA block copolymers. Solutions of Pull-b-PDMA displayed particles in cryo SEM. Moreover, an end group functionalization of Pull-b-PDMA with Rhodamine B allowed assessing the structure via LSCM and hollow spherical structures were observed indicating the presence of vesicles, too.
An exemplified pathway towards a DHBC based drug delivery vehicle was demonstrated with the block copolymer Pull-b-PVP. The block copolymer was synthesized via RAFT/MADIX techniques starting from a pullulan chain transfer agent. Pull-b-PVP displayed a concentration dependent self-assembly in water with an efficiency superior to the PEO-b-PVP system, which could be observed via DLS. Cryo SEM and LSCM microscopy displayed the presence of spherical structures. In order to apply a reversible crosslinking strategy on the synthesized block copolymer, the pullulan block was selectively oxidized to dialdehydes with NaIO4. The oxidation of the block copolymer was confirmed via SEC and 1H-NMR measurements. The self-assembled and oxidized structures were subsequently crosslinked with cystamine dihiydrochloride, a pH and redox responsive crosslinker resulting in crosslinked vesicles which were observed via cryo SEM. The vesicular structures of crosslinked Pull-b-PVP could be disassembled by acid treatment or the application of the redox agent tris(2-carboxyethyl)-phosphin-hydrochloride. The successful disassembly was monitored with DLS measurements.
To conclude, self-assembled structures from DHBCs such as particles and vesicles display a strong potential to generate an impact on biomedicine and nanotechnologies. The variety of DHBC compositions and functionalities are very promising features for future applications.
The nucleophilic thiol-ene (thia-Michael) reaction between molecular rods bearing terminal thiols and bis-maleimides was investigated. The molecular rods have oligospiroketal (OSK) and oligospirothioketal (OSTK) backbones. Contrary to the expectations, cyclic oligomers were always obtained instead of linear rigid-rod polymers. Replacing the OS(T)K rods with a flexible chain yielded polymeric products, suggesting that the OS(T) K structure is responsible for the formation of cyclic products. The reason for the preferred formation of cyclic products is due to the presence of folded conformations, which have already been described for articulated rods.
Polydepsipeptide Block-Stabilized Polyplexes for Efficient Transfection of Primary Human Cells
(2017)
The rational design of a polyplex gene carrier aims to balance maximal effectiveness of nucleic acid transfection into cells with minimal adverse effects. Depsipeptide blocks with an M (n) similar to 5 kDa exhibiting strong physical interactions were conjugated with PEI moieties (2.5 or 10 kDa) to di- and triblock copolymers. Upon nanoparticle formation and complexation with DNA, the resulting polyplexes (sizes typically 60-150 nm) showed remarkable stability compared to PEI-only or lipoplex and facilitated efficient gene delivery. Intracellular trafficking was visualized by observing fluorescence-labeled pDNA and highlighted the effective cytoplasmic uptake of polyplexes and release of DNA to the perinuclear space. Specifically, a triblock copolymer with a middle depsipeptide block and two 10 kDa PEI swallowtail structures mediated the highest levels of transgenic VEGF secretion in mesenchymal stem cells with low cytotoxicity. These nanocarriers form the basis for a delivery platform technology, especially for gene transfer to primary human cells.
The construction of nano-sized, two-dimensionally ordered nanoparticle (NP) superstructures is important for various advanced applications such as photonics, sensing, catalysis, or nano-circuitry. Currently, such structures are fabricated using the templated organization approach, in which the templates are mainly created by photo-lithography or laser-lithography and other invasive top-down etching procedures. In this work, we present an alternative bottom-up preparation method for the controlled deposition of NPs into hierarchical structures. Lamellar polystyrene-block-poly(2-vinylpyridinium) thin films featuring alternating stripes of neutral PS and positively charged P2VP domains serve as templates, allowing for the selective adsorption of negatively charged gold NPs. Dense NP assembly is achieved by a simple immersion process, whereas two-dimensionally ordered arrays of NPs are realized by microcontact printing (mu CP), utilizing periodic polydimethylsiloxane wrinkle grooves loaded with gold NPs. This approach enables the facile construction of hierarchical NP arrays with variable geometries. Copyright (C) 2016 John Wiley & Sons, Ltd.
The performance of organic photovoltaic blend devices is critically dependent on the polymer:fullerene interface. These interfaces are expected to impact the structural and thermal properties of the polymer with regards to the conjugated backbone planarity and transition temperatures during annealing/cooling processes. Here, we report the impact of fullerene intercalation on structural and thermal properties of poly(2,5-bis(3-tetradecylthiophen-2-yOthieno[3,2-b]thiophene (PBTTT), a highly stable material known to exhibit liquid crystalline behavior. We undertake a detailed systematic study of the extent of intercalation in the PBTTT:fullerene blend, considering the use of four different fullerene derivatives and also varying the loading ratios. Resonant Raman spectroscopy allows morphology in situ during controlled heating and cooling. We find that small fullerene molecules readily intercalate into PBTTT crystallites, resulting in a planarization of the polymer backbone, but high fullerene loading ratios or larger fullerenes result in nonintercalated domains. During cooling from melt, nonintercalated blend films are found to return to their original morphology and reproduce all thermal transitions on cooling with minimal hysteresis. Intercalated blend films show significant hysteresis on cooling due to the crystallized fullerene attempting to reintercalate. The strongest hysteresis is for intercalated blend films with excess fullerene loading ratio, which form a distinct nanoribbon morphology and exhibit a reduced geminate recombination rate. These results reveal that careful consideration should be taken during device fabrication, as postdeposition thermal treatments significantly impact the charge generation and recombination dynamics.