Preparation and applications of periodical gold nanoparticle arrays

Diese Arbeit beschäftigt sich mit der Herstellung und Anwendungen von periodischen Goldnanopartikel-Arrays (PPAs), die mit Hilfe von Nanosphären-Lithografie hergestellt wurden. In Abhängigkeit der verwendeten Nanosphären-Größe wurden dabei entweder kleine dreieckige Nanopartikel (NP) (bei Verwendung von Nanosphären mit einem Durchmesser von 330 nm) oder große dreieckige NPD sowie leicht gestreckte NP (bei Verwendung von Nanosphären mit einem Durchmesser von 1390 nm) hergestellt. Die Charakterisierung der PPAs erfolgte mit Hilfe von Rasterkraftmikroskopie, Rasterelektronenmikroskopie und optischer Spektroskopie. Die kleinen NP besitzen ein Achsverhältnis (AV) von 2,47 (Kantenlänge des NPs: (74+/-6) nm, Höhe: (30+/-4) nm. Die großen dreieckigen NP haben ein AV von 3 (Kantenlänge des NPs:(465+/-27) nm, Höhe: (1530+/-10) nm) und die leicht gestreckten NP (die aufgrund der Ausbildung von Doppelschichten ebenfalls auf der gleichen Probe erzeugt wurden) haben eine Länge von (364+/-16)nm, eine Breite von (150+/-20) nm und eine Höhe von (150+/-10)nm. Die optischen Eigenschaften dieser NP werden durch lokalisierte Oberflächenplasmon-Polariton Resonanzen (LPPRs) dominiert, d.h. von einem eingestrahlten elektromagnetischen Feld angeregte kollektive Schwingungen der Leitungsbandelektronen. In dieser Arbeit wurden drei signifikante Herausforderungen für Plasmonik-Anwendungen bearbeitet, welche die einzigartigen optischen Eigenschaften dieser NP ausnutzen. Erstens wurden Ergebnisse der selektiven und präzisen Größenmanipulation und damit einer Kontrolle der interpartikulären Abstände von den dreieckigen Goldnanopartikel mit Hilfe von ns-gepulstem Laserlicht präsentiert. Die verwendete Methode basiert hierbei auf der Größen- und Formabhängigkeit der LPPRs der NP. Zweitens wurde die sensorischen Fähigkeiten von Gold-NP ausgenutzt, um die Bildung von molekularen Drähten auf den PPAs durch schrittweise Zugabe von unterschiedlichen molekularen Spezies zu untersuchen. Hierbei wurde die Verschiebung der LSPPR in den optischen Spektren dazu ausgenutzt, die Bildung der Nanodrähte zu überwachen. Drittens wurden Experimente vorgestellt, die sich die lokale Feldverstärkung von NP zu nutze machen, um eine hochgeordnete Nanostrukturierung von Oberflächen mittels fs-gepulstem Laserlicht zu bewerkstelligen. Dabei zeigt sich, dass neben der verwendeten Fluenz die Polarisationsrichtung des eingestrahlten Laserlichts in Bezug zu der NP-Orientierung sowie die Größe der NP äußerst wichtige Parameter für die Nanostrukturierung darstellen. So konnten z.B. Nanolöcher erzeugt werden, die bei höheren Fluenzen zu Nanogräben und Nanokanälen zusammen wuchsen. Zusammengefasst lässt sich sagen, dass die in dieser Arbeit gewonnen Ergebnisse von enormer Wichtigkeit für weitere Anwendungen sind.

Verbal proficiency as fitness indicator: Experimental and comparative research on the evolutionary psychology of language and verbal displays

Summary: Recent research on the evolution of language and verbal displays (e.g., Miller, 1999, 2000a, 2000b, 2002) indicated that language is not only the result of natural selection but serves as a sexually-selected fitness indicator that is an adaptation showing an individual’s suitability as a reproductive mate. Thus, language could be placed within the framework of concepts such as the handicap principle (Zahavi, 1975). There are several reasons for this position: Many linguistic traits are highly heritable (Stromswold, 2001, 2005), while naturally-selected traits are only marginally heritable (Miller, 2000a); men are more prone to verbal displays than women, who in turn judge the displays (Dunbar, 1996; Locke & Bogin, 2006; Lange, in press; Miller, 2000a; Rosenberg & Tunney, 2008); verbal proficiency universally raises especially male status (Brown, 1991); many linguistic features are handicaps (Miller, 2000a) in the Zahavian sense; most literature is produced by men at reproduction-relevant age (Miller, 1999). However, neither an experimental study investigating the causal relation between verbal proficiency and attractiveness, nor a study showing a correlation between markers of literary and mating success existed. In the current studies, it was aimed to fill these gaps. In the first one, I conducted a laboratory experiment. Videos in which an actor and an actress performed verbal self-presentations were the stimuli for counter-sex participants. Content was always alike, but the videos differed on three levels of verbal proficiency. Predictions were, among others, that (1) verbal proficiency increases mate value, but that (2) this applies more to male than to female mate value due to assumed past sex-different selection pressures causing women to be very demanding in mate choice (Trivers, 1972). After running a two-factorial analysis of variance with the variables sex and verbal proficiency as factors, the first hypothesis was supported with high effect size. For the second hypothesis, there was only a trend going in the predicted direction. Furthermore, it became evident that verbal proficiency affects long-term more than short-term mate value. In the second study, verbal proficiency as a menstrual cycle-dependent mate choice criterion was investigated. Basically the same materials as in the former study were used with only marginal changes in the used questionnaire. The hypothesis was that fertile women rate high verbal proficiency in men higher than non-fertile women because of verbal proficiency being a potential indicator of “good genes”. However, no significant result could be obtained in support of the hypothesis in the current study. In the third study, the hypotheses were: (1) most literature is produced by men at reproduction-relevant age. (2) The more works of high literary quality a male writer produces, the more mates and children he has. (3) Lyricists have higher mating success than non-lyric writers because of poetic language being a larger handicap than other forms of language. (4) Writing literature increases a man’s status insofar that his offspring shows a significantly higher male-to-female sex ratio than in the general population, as the Trivers-Willard hypothesis (Trivers & Willard, 1973) applied to literature predicts. In order to test these hypotheses, two famous literary canons were chosen. Extensive biographical research was conducted on the writers’ mating successes. The first hypothesis was confirmed; the second one, controlling for life age, only for number of mates but not entirely regarding number of children. The latter finding was discussed with respect to, among others, the availability of effective contraception especially in the 20th century. The third hypothesis was not satisfactorily supported. The fourth hypothesis was partially supported. For the 20th century part of the German list, the secondary sex ratio differed with high statistical significance from the ratio assumed to be valid for a general population.

Adsorption kinetic investigations of phthalocyanine derivatives self assembled monolayers (SAMs) on gold: Temperature influence on the SAM formation process and quality

The ordered nano-structured surfaces, like self-assembled monolayers (SAMs) are of a great scientific interest, due to the low cost, simplicity, and versatility of this method. SAMs found numerous of applications in molecular electronics, biochemistry and optical devices. Phthalocyanine (Pc) complexes are of particular interest for the SAM preparation. These molecules exhibit fascinating physical properties and are chemically and thermally stable. Moreover their complex structure is advantageous for the fabrication of switchable surfaces. In this work the adsorption process of Pcs derivatives, namely, subphthalocyanines (SubPcB) and terbium (2TbPc) sandwich complexes on gold has been investigated. The influence of the molecular concentration, chain length of peripheral groups, and temperature on the film formation process has been examined using a number of techniques. The SAMs formation process has been followed in situ and in real time by means of second harmonic generation (SHG) and surface plasmon resonance (SPR) spectroscopy. To investigate the quality of the SAMs prepared at different temperatures atomic force microscopy (AFM) and X-Ray photoelectron spectroscopy (XPS)measurements were performed. Valuable information about SubPcB and 2TbPc adsorbtion process has been obtained in the frame of this work. The kinetic data, obtained with SHG and SPR, shows the best conformance with the first order Langmuir kinetic model. Comparing SHG and SPR results, it has been found, that the film formation occurs faster than the formation of chemical bonds. Such, the maximum amount of molecules on the surface is reached after 6 min for SubPcB and 30 min for 2TbPc. However, at this time the amount of formed chemicals bonds is only 10% and 40% for SubPcB and 2TbPc, respectively. The most intriguing result, among others, was obtained at T = 2 °C, where the formation of the less dense SAMs have been detected with SHG.However, analyzing XPS and AFM data, it has been revealed, that there is the same amount of molecules on the surface at both temperature T = 2 °C, and T = 21 °C, but the amount of formed chemicals bond is different. At T = 2 °C molecules form aggregates, therefore many of available anchor groups stay unattached.