Quantum chemical studies on lowcoordinated group 14-16 compounds have been performed. This thesis focuses particularly on silenes influenced by reverse Siδ-=Cδ+ bond polarization. Hypercoordinated carbon compounds are also studied. The geometries from calculations with several common computationally inexpensive methods have been tested against high level CCSD/cc-pVTZ geometries for a series of substituted silenes. Hybrid HF/DFT methods performed best among the inexpensive methods tested for silenes. Heavy alkenes strongly influenced by reverse polarization are found to have less exothermic dimerization energies for both head-to-head and head-to-tail dimerizations, and to have higher activation energies for water addition than naturally polarized heavy alkenes. We also investigated solvated lithium, magnesium and potassium silenolates and found that lithium and magnesium ions coordinate preferably to O, giving their SiC bond some double bond character. Reverse polarized 2-siloxy-, 2-thiosiloxy-, and 2-(N-sila-N-methyl)-silenes could according to calculations be formed thermolytically from the corresponding tetrasilanes as transient species. It was, however, found that silenes highly influenced by π-conjugative reverse polarization have low barriers for the back-reaction, and thus these silenes are more difficult to form as stable species than naturally polarized silenes. It is also found that conjugated 1-siladienes, formed by electrocyclic ring-opening of 1-silacyclobut-2-enes, which are highly influenced by π-conjugative reverse polarization, have higher barriers for electrocyclization back to starting material than naturally polarized 1-siladienes. It is found that CHe54+, CHe64+, CNe54+, and CNe64+ are the closest carbon analogs of SiH5-, SiH62-, SiF5- and SiF62-, respectively. However, due to their exothermic dissociation reaction, these very high-lying local minima will be impossible to reach experimentally.

This research presents advancements in the coupling of capillary electrochromatography (CEC) to mass spectrometry (MS) for the analysis of different chemical classes of surfactants. Chapter 1 provides a brief introduction that summarizes the mechanics and fundamentals of CEC, including instrumentation and applications for CEC-MS. Chapter 2 describes the on-line hyphenation of a packed CEC column with an internally tapered tip coupled to electrospray ionization-mass spectrometry (ESI-MS) and atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) for the analysis of betaine-type amphoteric or zwitterionic surfactants (Zwittergent®). The interesting aspects include CEC-MS column manufacture and charaterization, as well as a comparison between the CEC-ACPI-MS and CEC-ESI-MS ionization pattern of zwittergents. In Chapter 3, the CEC-MS of alkyltrimethyl-ammonium ions (ATMA+) with chain length ranging from C1-C18 is optimized using an internally tapered CEC-MS column packed with mixed mode C6/strong cation exchange stationary phase and coupled to an ESI source. In addition, the optimized CEC-ESI-MS protocol is applied for the challenging analysis of commercial sample Arquad S-50 ATMA+ containing cis-trans unsaturated and saturated soyabean fatty acid derivatives. In Chapter 4, a novel CEC-UV method for separation of the various Triton X-100 oligomers is presented. A systematic mobile phase tuning and comparison of monomeric vs. polymeric stationary phases was conducted. In Chapter 5, we present the first application of CEC coupled to MS for analysis of Triton X (TX-) series surfactants. A characterization from the viewpoint of the ion and adduct formation for TX-series nonionic surfactants with a variable number of ethoxy units (n=1.5-16) in the scan mode are first discussed. Next, utilizing the TX-series as model alkylphenolpolyethoxylates (APEOs), a detailed investigation of the chromatographic separation and MS detection are performed followed by analysis of very long chain TX series with n=30-70. In Chapter 6, CEC-MS utilizing full scan positive ion mode of ESI was employed to study the effect of fragmentor voltage on the in-source collision induced dissociation (IS-CID) of several APEO nonionic surfactants. Finally, in Chapter 7, the preparation and characterization of a novel liquid crystalline stationary phase suitable for separation of neutral and charged compounds in packed column CEC is evaluated.

Entre as mais importantes propriedades de soluções aquosas micelares está a capacidade de incorporar substâncias orgânicas com diferentes polaridades e graus de hidrofobicidade. Como demonstrado por Quina et aI. (J Phys. Chem., 1995, 99, 11708-11714), um dos métodos mais promissores para a obtenção de correlações entre e a eficiência de solubilização em micelas e as estruturas do soluto e do detergente é através do uso de relações lineares de energia livre (LSERs). No presente trabalho, investigou-se a incorporação de uma série de solutos neutros em micelas dos detergentes zwitteriônicos dimetil-hexadecilamônio-propano sulfonato (CDAPS; 31 solutos) e o N-óxido de dimetil-dodecilamina (DDAO; 33 solutos), bem como em micelas catiônicas da forma protonada de DDAO (DDAOH+; 33 solutos). As constantes de incorporação dos solutos foram determinadas experimentalmente por meio de técnicas fotofísicas, métodos de solubilização e cromatografia líquida e gasosa. A análise dos resultados foi efetuada através de técnicas de regressão múltipla, obtendo-se as seguintes LSERs: CDAPS: Log Ks = - 0,55 + 0,99 R2 - 0,82 π2 + 0,36 Σα2 - 0,99 Σβ2 + 2,73 Vx DDAOH+: Log Ks = - 0,68 + 1,30 R2 - 0,78 π2 + 0,67 Σα2 - 1,45 Σβ2 + 2,29 Vx DDAO: Log Ks = - 0,46 + 0,89 R2 - 0,61 π2 + 0,82 Σα2 - 1,66 Σβ2 + 2,59 Vx onde Σα2 e Σβ2 representam a \"acidez\" e a \"basicidade\" do soluto, com relação à formação de pontes de hidrogênio, R2 corresponde à refração molar em excesso, π2 representa a dipolaridade e Vx é o volume molar do soluto. As LSERs obtidas indicam que os detergentes zwitteriônicos formam sistemas distintos dos demais estudados até o momento. No entanto, os sistemas DDAO e DDAOH+ apresentam LSERs muito semelhantes entre sí, sugerindo que a incorporação dos solutos não é afetada por uma mudança da estrutura (carga) da cabeça do detergente. / One of the most important properties of aqueous micellar solutions is their capacity to incorporate organic solutes with different degrees of polarity and hydrophobicity. As demonstrated by Quina et aI. (J. Phys. Chem., 1995, 99, 1170811714), one of the most promissing methods for obtaining correlations between solubilization eficiency and the solute and surfactant structure is via the use of linear solvation energy relationships (LSERs). The present work investigates the incorporation of a series of neutral solutes in micelles of the zwitterionic detergents hexadecyldimethylammonium propanesulfonate (CDAPS; 31 solutes) and the N-oxide of dodecyldimethylamine (DDAO; 33 solutes), as well as in the cationic micelles of the protonated form of DDAO (DDAOH+; 33 solutes). The incorporation constants were determined experimentally by photophysical techniques, from solubility measurements and by liquid and gas chromatographic methods. Analysis of the results by multiple regression techniques led to the following LSERs: CDAPS: Log Ks = - 0,55 + 0,99 R2 - 0,82 π2 + 0,36 Σα2 - 0,99 Σβ2 + 2,73 Vx DDAOH+: Log Ks = - 0,68 + 1,30 R2 - 0,78 π2 + 0,67 Σα2 - 1,45 Σβ2 + 2,29 Vx DDAO: Log Ks = - 0,46 + 0,89 R2 - 0,61 π2 + 0,82 Σα2 - 1,66 Σβ2 + 2,59 Vx where Σα2 and Σβ2 are the hydrogen bond acidity and basicity of the solute, R2 is the excess molar refraction, π2 is the dipolarity and Vx corresponds to the molar volume of the solute. The LSERs obtained demonstrate that zwitterionic surfactants are distinct from the other systems investigated previously. However, the similarity of the LSERs of DDAO and DDAOH+ suggests that incorporation of solutes is not affected by changes in the structure (charge) ofthe polar headgroup.

Title: The study on interactions of functional surfaces with biological systems Author: Ivana Víšová Department: Institute of Physics of the Czech Academy of Sciences, Department of optical and biophysical systems. Supervisor: RNDr. Hana Vaisocherová-Lísalová, Ph.D., Institute of Physics of the Czech Academy of Sciences, Department of optical and biophysical systems. Abstract: This work is devoted to the study of processes influencing the performance of functional antifouling polymer brush coatings and their interactions with complex biological media. Specifically, both results of the fundamental and applied research on the i) functionalization processes influencing coating resistance, ii) tailoring of the physico-chemical properties of the antifouling coatings to minimize the nonspecific interactions with complex biological samples, and iii) behavior and performance of the polymer brush coatings in varying environments are presented. Acrylamide and methacrylamide-based polymer brushes with side hydroxyl, carboxybetaine, and sulfobetaine groups were studied, showing the great potential of their optimized copolymer structures as tunable antifouling functionalizable platforms for cell research or biosensor applications. Moreover, newly developed procedures for antifouling properties recovery after EDC/NHC...

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Membranas e organelas constituem estruturas presentes nas células dos organismos. Estas estruturas representam interfaces entre eletrólitos. Uma tentativa de descrever, interpretar e compreender a distribuição iônica nas vizinhanças destas estruturas é feita neste trabalho com a análise de resultados de experimentos obtidos na investigação de alguns sistemas: 1) Sistemas constituídos por micelas de SDS. Medidas do pH nas vizinhanças de superfícies das micelas por sondas derivadas do ácido salicílico mostra variações do pH em termos da concentração de SDS e da concentração de sal adicionado. O objetivo dos experimentos é inferir o comportamento do pH nas vizinhanças de membranas biológicas que, por dissociação de alguns fosfolipídios, podem apresentar segmentos da membrana com carga na superfície. 2) A natureza \"zwitteriônica\" das membranas biológicas motivou o estudo da \"ligação iônica\" em micelas \"zwitteriônicas\", imersas em soluções com eletrólito, em concentrações variadas de sais de Cl- e Br- com os cátions monovalentes, Li+, Na+, K+, Rb+, Cs+ e tetrametil amônio (TMA+) e bivalentes Mg2+ e Ca2+. Os experimentos consistiram em determinar a concentração de haletos próximos a micela. A técnica de captura química mostra que há um grau de seletividade que não é determinado apenas pela carga iônica. 3) Resultados preliminares do grau de dissociação no interior de vesiculas de, cloreto de dimetildioctadecil amônio, DODAC, indicam que 8% dos monômeros estão dissociados em vesículas com o diâmetro médio em torno de 150 e 300 nm. As leis fundamentais usadas para compreender os resultados estão aliadas a hipótese de que os sistemas estudados estão em equilibrio termodinâmico, que a interação eletrostática é predominante e ao potencial eletrostático é conferido o papel do potencial da força média que atua nos íons. A simplificação adicional consistindo em admitir que os íons se comportam como cargas puntiformes no que se refere à interação eletrostática conduz o modelo teórico à equação de Poisson-Boltzmann que, linearizada, resulta na equação de Debye-Hückel. Hipóteses adicionais se fazem necessárias para formular o modelo como um problema matemático com condições de contorno. Para cada situação as hipóteses adicionais são discutidas. Sistemas hipotéticos são analizados com o intuito de comparar os resultados provenientes da equação de Poisson-Boltzmann e da equação de Debye-Hückel. A análise teórica dos sistemas conduz a resultados em acordo com os valores medidos. Entre as conclusões obtidas, neste trabalho, são mencionados: 1- As sondas derivadas do ácido salicílico mantêm os grupos dissociáveis próximos a superfície, a distância é da ordem de 0,1 nm, mesmo para sondas que apresentam cadeia longa entre o grupo nitrogênio e o grupo dissociável. 2- A especificidade iônica é bem descrita utilizando, além da carga elétrica, a massa do íon. Os íons na superfície de uma micela zwitteriônica têm liberdade translacional e portanto superfícies zwitteriônicas em solução de eletrólito apresentam condutividade elétrica na superfície. 3- As concentrações iônicas no interior de vesículas são uniformes em praticamente toda a região interna, apresentando variações apenas nas vizinhanças da superfície interna carregada eletricamente. / Membranes and organelles are structures present in biological systems. Such structures are interfaces between electrolytes. Addressing to the description, interpretation and comprehension of the ionic distribution around the structures an attempt is done is this work analyzing experimental results from the investigation of the following systems: 1) SDS micelles. \"pH\" measurements in the micellar surface neighborhood using salicylic acid probes show the pH values dependence with the SDS and added salt concentrations. The experiments aimed to infer the pH behavior in biological membranes where same phospholipids may dissociate and portions of the surface can acquire electrical charges. 2) The zwitterionic nature of biological membranes leads to the investigation of ion binding in zwitterionic micelles in electrolyte solutions with varied concentrations of Cl- or Br<SUP- salts with the cations Li+, Na+, K+, Rb+, Cs+ e tetramethylammonium (TMA+) and the bivalent cations Mg2+ e Ca2+. Halide concentration in the micellar vicinity was measured. Chemical trapping method shows there is a selectivity degree that does not depend only on the ionic charge. 3) Preliminary results in the determination of the inner dissociation degree of dioctadecyldimethylammonium chloride vesicles, DODAC, show that about 8% of the vesicle constituent monomers are dissociated in vesicles with 150 and 300 nm mean diameter. The theoretical description is based upon the thermodynamics equilibrium hypothesis about the systems and that the electrostatic interaction is the stronger interaction and also it is attributed to the mean electrostatic potential the role of the mean force potential acting on the ionic species. A further simplification in considering the ions as point charges with respect to the electrostatic interactions leads the model to the Poisson-Boltzmann equation and under linearization results in the Debye-Hückel alternative description. Additional hypothesis are necessary in order to have the model as a mathematical problem with boundary conditions and are discussed for each system. Hypothetical systems are analysed aiming the comparison between Poisson-Boltzmann and Debye- Hückel descriptions. Some conclusions derived in the analysis are: 1- The salicylic acid probes have the dissociable groups always near (~0,1nm) the micellar surface, even to the probes that have a long chain between the nitrogen group and the dissociable group. 2- In a zwitterionic micelle the ions on the surface have translational freedom and this is way the zwitterionic membranes in electrolyte solutions are conducting surfaces. 3- The ionic concentrations in the vesicle interior have uniformly value almost everywhere showing variations only in the vicinity of the electrically charged interior surface. The theoretical study of the three systems considered gives results in accord with experimental data.

Zum ersten Mal wurden neuartige photoaktive heterocyclische Spiroacridane synthetisiert und deren photochemische Ringöffnungsreaktion, die zur Bildung bipolarer Acridiniumverbindungen führt, untersucht. Die Zwitterione reagierten ihrerseits thermisch zu den ursprünglichen Spiroacridanen zurück. Die Reproduzierbarkeit des Schalvorgangs wurde jedoch durch eine Nebenreaktion zum 9-H-9-aryl-acridan mit einer Aldehydfunktion im Seitenarm begrenzt. Diese unerwünschte Reaktion konnte durch die Substitution der Protonen der Methylengruppe am Sauerstoff durch Methylgruppen unterbunden werden. Jetzt funktioniert das reversible photochrome System. Je nach der Zusammensetzung des Lösungsmittels und der Größe des Ringes, liegen die Lebensdauer der Zwitterionen im Millisekunden- bis Sekundenbereich. Der Schaltvorgang konnte auch chemisch durch die abwechselnde Zugabe einer Säure und einer Base realisiert werden. Des Weiteren wurde die Spiroacridan-Einheit zu den molekularen Achsen ausgebaut, um ein Rotaxan mit dem Makrocyclus Cyclobis(paraquat-p-phenylen) herzustellen. Der Makrocyclus pendelt zwischen der Alkoxy-phenyl-Ausweichstation und der Spiroacridan-Station, hält sich aber wegen der sterischen Hinderung durch die im Pyranring des Spiroacridans anwesenden Methylgruppen hauptsächlich auf der ersten Station auf. Das Spiroacridan innerhalb des Rotaxans wurde photochemisch unter Bildung der bipolaren Acridiniumstation geöffnet. Gemäß MM2-Berechnungen befindet sich der Makrocyclus bevorzugt auf dem gebildeten Zwitterion wegen der Anziehung zwischen dem negativ geladenen Alkoxid-Seitenarm der 9-Aryl-acridinium-Einheit und dem tetrakationischen Ring. Die Translation des Makrocyclus kann auch durch die Zugabe von Säure oder Base kontrolliert werden. / For the first time we synthesized novel photoactive heterocyclic spiro-acridanes and studied their photochemical ring opening that leads to bipolar acridinium compounds; these, in turn, could thermally react to return to the spiro-acridane moiety. However, a side reaction via the photoexcited state resulted in 9-H-9-aryl-acridanes with an aldehyde side arm. This undesired reaction could be avoided by substituting the hydrogen atoms neighbouring the oxygen atom by methyl groups. With this enhancement a reversible photochromic system works. Depending on the solvent and the ring size, the lifetime of the zwitterions is in the range of milliseconds to seconds. The switching cycle could also be realized by the alternating addition of acid and base. The spiro-acridane unit was introduced into a molecular axle in order to construct a rotaxane using the wheel of cyclobis(paraquat-p-phenylene). The wheel shuttles between an alkoxy-phenyl-unit as evasive recognition station and the spiro-acridane station; but resides mainly on the first station because of the steric interference with the methyl groups present in the pyrane ring of the spiro-acridane. The spiro-acridane within the rotaxane was photochemically opened to give a rotaxane with a bipolar acridinium station. Calculations (MM2-level) suggest that the ring resides on the zwitterions due to the attraction between the negatively charged side-arm of the 9-aryl-acridinium unit and the positive charges of the wheel. The movement of the ring component can also be controlled by acid and base addition.

<p>Liquid Chromatography (LC) and Capillary Electrophoresis (CE) are modern analytical techniques that play very important roles in many areas of modern science such as life science, biotechnology, biomedicine, environmental studies, and development of pharmaceutics. Even though these two techniques have existed and been subjected to studies for several decades, the developments of new separation materials for them are still very important till now in order to meet the different new demands for improvement from other disciplines in science.</p><p>In this doctoral thesis, several novel covalently bonded sulfobetaine type zwitterionic separation materials are synthesized for the application in LC and CE. These materials carry both positively charged quaternary ammonium groups and negatively charged sulfonic groups, which result in a very low net surface charge compared to conventional separation materials with only anionic or cationic functional groups. Consequently, it is possible to employ these materials for separation of different ionic species under mild conditions. The surface properties have also been characterized, mainly by elemental analysis, sorption isotherm, ζ-potential measurements, and spectroscopic methods.</p><p>By using packed zwitterionic columns for liquid chromatography, small inorganic anions or cations, and acidic or basic proteins can be independently and simultaneously separated in a single run using optimal sets of separation conditions. This is a unique property compared to conventional ionic separation material for LC. When fused silica capillaries coated with zwitterionic polymer are used for capillary electrophoresis, good separations can be achieved for solutes as different as inorganic anions, peptides, proteins, and tryptically digested proteins.</p>

Weltweit versuchen Wissenschaftler, künstliche Viren für den Gentransfer zu konstruieren, die nicht reproduktionsfähig sind. Diese sollen die Vorteile der natürlichen Viren besitzen (effizienter Transport von genetischem Material), jedoch keine Antigene auf ihrer Oberfläche tragen, die Immunreaktionen auslösen. <br><br> Ziel dieses Projektes ist es, einen künstlichen Viruspartikel herzustellen, dessen Basis eine Polyelektrolytenhohlkugel bildet, die mit einer Lipiddoppelschicht bedeckt ist. Um intakte Doppelschichten zu erzeugen, muss die Wechselwirkung zwischen Lipid und Polyelektrolyt (z.B. DNA) verstanden und optimiert werden. Dazu ist es notwendig, die strukturelle Grundlage der Interaktion aufzuklären. Positiv geladene Lipide gehen zwar starke Wechselwirkungen mit der negativ geladenen DNA ein, sie wirken jedoch toxisch auf biologische Zellen. In der vorliegenden Arbeit wurde daher die durch zweiwertige Kationen vermittelte Kopplung von genomischer oder Plasmid-DNA an zwitterionische oder negativ geladene Phospholipide an zwei Modellsystemen untersucht. <br><br> 1. Modellsystem: Lipidmonoschicht an der Wasser/Luft-Grenzfläche <br> Methoden:<br> Filmwaagentechnik in Kombination mit IR-Spektroskopie (IRRAS), Röntgenreflexion (XR), Röntgendiffraktion (GIXD), Brewsterwinkel-Mikroskopie (BAM), Röntgenfluoreszenz (XRF) und Oberflächenpotentialmessungen <br> Resultate:<br> A) Die Anwesenheit der zweiwertigen Kationen Ba2+, Mg2+, Ca2+ oder Mn2+ in der Subphase hat keinen nachweisbaren Einfluss auf die Struktur der zwitterionischen DMPE- (1,2-Dimyristoyl-phosphatidyl-ethanolamin) Monoschicht. <br> B) In der Subphase gelöste DNA adsorbiert nur in Gegenwart dieser Kationen an der DMPE-Monoschicht. <br> C) Sowohl die Adsorption genomischer Kalbsthymus-DNA als auch der Plasmid-DNA pGL3 bewirkt eine Reduktion des Neigungswinkels der Alkylketten, die auf einen veränderten Platzbedarf der Kopfgruppe zurückzuführen ist. Durch die Umorientierung der Kopfgruppe wird die elektrostatische Wechselwirkung zwischen den positiv geladenen Stickstoffatomen der Lipidkopfgruppen und den negativ geladenen DNA-Phosphaten erhöht.<br> D) Die adsorbierte DNA weist eine geordnete Struktur auf, wenn sie durch Barium-, Magnesium-, Calcium- oder Manganionen komplexiert ist. Der Abstand zwischen parallelen DNA-Strängen hängt dabei von der Größe der DNA-Fragmente sowie von der Art des Kations ab. Die größten Abstände ergeben sich mit Bariumionen, gefolgt von Magnesium- und Calciumionen. Die kleinsten DNA-Abstände werden durch Komplexierung mit Manganionen erhalten. Diese Ionenreihenfolge stellt sich sowohl für genomische DNA als auch für Plasmid-DNA ein. <br> E) Die DNA-Abstände werden durch die Kompression des Lipidfilms nicht beeinflusst. Zwischen der Lipidmonoschicht und der adsorbierten DNA besteht demnach nur eine schwache Wechselwirkung. Offensichtlich befindet sich die durch zweiwertige Kationen komplexierte DNA als weitgehend eigenständige Schicht unter dem Lipidfilm. <br> <br><br> 2. Modellsystem: Lipiddoppelschicht an der fest/flüssig-Grenzfläche<br> Methoden:<br> Neutronenreflexion (NR) und Quarzmikrowaage (QCM-D)<br> Resultate:<br> A) Das zwitterionische Phospholipid DMPC (1,2-Dimyristoyl-phosphatidylcholin) bildet keine Lipiddoppelschicht auf planaren Polyelektrolytmultischichten aus, deren letzte Lage das positiv geladene PAH (Polyallylamin) ist. <br> B) Hingegen bildet DMPC auf dem negativ geladenen PSS (Polystyrolsulfonat) eine Doppelschicht aus, die jedoch Defekte aufweist. <br> C) Eine Adsorption von genomischer Kalbsthymus-DNA auf dieser Lipidschicht findet nur in Gegenwart von Calciumionen statt. Andere zweiwertige Kationen wurden nicht untersucht.<br> D) Das negativ geladene Phospholipid DLPA (1,2-Dilauryl-phosphatidsäure) bildet auf dem positiv geladenen PAH eine Lipiddoppelschicht aus, die Defekte aufweist. <br> E) DNA adsorbiert ebenfalls erst in Anwesenheit von Calciumionen in der Lösung an die DLPA-Schicht.<br> F) Durch die Zugabe von EDTA (Ethylendiamintetraessigsäure) werden die Calciumionen dem DLPA/DNA-Komplex entzogen, wodurch dieser dissoziiert. Demnach ist die calciuminduzierte Bildung dieser Komplexe reversibel. / All over the world scientists are trying to engineer artificial viruses, which do not replicate, for gene delivery. These artificial viruses should have the advantages of natural viruses such as efficient transport of genetic material, but they should not carry antigens, which cause immune reactions, on their top portion.<br><br> The aim of this project is to develop an artificial virus particle that is based on a polyelectrolyte hollow capsule which is covered by a lipid bilayer. To create intact bilayers, it is crucial to understand and optimize the interaction between lipids and polyelectrolytes (e. g. DNA). Therefore the structural basis of that interaction must be elucidated. Positively charged lipids interact strongly with the negatively charged DNA but they cause toxic reactions in biological cells. Hence the present work used two model systems to study the coupling of genomic or plasmid DNA to zwitterionic or negatively charged phospholipids induced by divalent cations. <br><br> 1. Model system: Lipid monolayer at the air/water-interface <br> Methods: <br> Langmuir filmbalance in combination with IR-spectroscopy (IRRAS), X-ray reflectometry (XR), X-ray diffraction (GIXD), Brewster angle microscopy (BAM), X-ray fluorescence (XRF), and surface potential measurements<br> Results:<br> A) The presence of the divalent cations Ba2+, Mg2+, Ca2+ or Mn2+ in the subphase has no traceable influence on the structure of a zwitterionic DMPE (1,2-dimyristoyl-phosphatidyl-ethanolamine) monolayer.<br> B) DNA which is dissolved in the subphase adsorbs to the DMPE-monolayer only if divalent cations are present.<br> C) The adsorption of genomic calf thymus DNA as well as of the plasmid DNA pGL3 causes a reduction of the tilt angle of the lipid alkyl chains. The tilt reduction can be ascribed to a change in the space required by the lipid head group. This change in head group orientation increases the electrostatic interaction between the positively charged nitrogen atoms in the lipid head and the negatively charged DNA phosphates.<br> D) The adsorbed DNA exhibits an ordered structure if it is complexed by barium, magnesium, calcium or manganese ions. The spacing between parallel DNA strands depends on the size of the DNA fragments as well as on the kind of cation. The largest DNA-spacings are observed with barium ions, followed by magnesium and calcium ions. DNA-complexation with manganese ions causes the smallest spacings. This order of ions is observed for both genomic and plasmid DNA.<br> E) Compression of the monolayer does not influence the DNA spacings. Thus the interaction between the lipid monolayer and adsorbed DNA is only weak. The DNA must exist as a more or less separate layer under the lipid film.<br> <br><br> 2. Model system: Lipid bilayer at the solid/fluid-interface<br> Methods: <br> Neutron reflectometry (NR), and Quartz crystal microbalance (QCM-D)<br> Results:<br> A) The zwitterionic phospholipid DMPC (1,2-dimyristoyl phosphatidylcholine) does not form lipid bilayers on top of planar polyelectrolyte multilayers covered with the positively charged PAH (polyallylamine).<br> B) In contrast, DMPC forms a lipid bilayer with defects on top of the negatively charged PSS (polystyrolsulfonate) terminated polyelectrolyte cushion.<br> C) Genomic calf thymus DNA adsorbs only to the DMPC layer in presence of calcium ions. Different ions were not examined.<br> D) The negatively charged phospholipid DLPA (1,2-dilauryl-phosphatidic acid) also forms a lipid bilayer with defects on top of the PAH-terminated cushion.<br> E) The DNA adsorbs also to the DLPA layer only in the presence of calcium ions in the solution.<br> F) By addition of EDTA (ethylenediaminetretraacetic acid) the calcium cations are removed from the DLPA/DNA-complex and the complex dissociates. Thus the calcium induced formation of that complex is reversible.<br><br>