Remarks on Parametric Surface Waves in a Nonlinear and Non-Ideally Excited Tank

We studied free surface oscillations of a fluid in a cylinder tank excited by an electric motor with limited power supply. We investigated the possibility of parametric resonance in this system, showing that the excitation mechanism can generate chaotic response. Numerical experiments are carried out to present the existence of several types of regular and chaotic attractors. For the first time powers (power of the motor, power consumed by the damping force under fluid free surface oscillations, and a total power) are calculated, investigated, and shown for different regimes, regular and chaotic ones for parametric resonance interactions. [DOI: 10.1115/1.4005844]

Single-wall carbon nanotube interactions with copper-oxamato building block of molecule-based magnets probed by resonance Raman spectroscopy

The electronic interactions between the [Cu(opba)]2- anions (where opba is orthophenylenebis (oxamato)) and single-wall carbon nanotubes (SWCNTs) were investigated by resonance Raman spectroscopy. The opba can form molecular magnets, and the interactions of opba with SWCNTs can produce materials with very different magnetic/electronic properties. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes. The interaction also is dependent on the amount of complex that is probably adsorbed on the carbon surface of the SWCNTs. Some charge transfer can be also occurring between the metallic complex and the SWCNTs. Copyright (c) 2012 John Wiley & Sons, Ltd.

Surface-functionalized latex particles as additives in the mineralization of zinc oxide

Polystyrene latex particles modified at the surface with different hydrophilic functional groups were prepared by miniemulsion polymerization and applied to control the crystallization of zinc oxide in aqueous medium. The effects of both latex structure and concentration on the crystal growth, morphology, crystalline structure, and properties of the resulting zinc oxide were analyzed. Depending on the latex additive used, micro- and submicrosized crystals with a broad variety of morphologies were obtained. Among the studied latexes, the carboxyl-derived particles were shown to be a convenient system for further quantitative investigations. In this case, as the additive concentration increases, the aspect ratio of the crystals decreases systematically. Latex particles are assumed to adsorb preferentially onto the fast growing {001} faces of ZnO, interacting with the growth centers and reducing the growth rate in [001]. When zinc oxide is precipitated in the presence of latex, the polymer particles become incorporated into the growing crystals and polymer–inorganic hybrid materials are obtained. These materials are composed of an inorganic and largely undisturbed crystalline matrix in which organic latex particles are embedded. Increasing amounts of latex become incorporated into the growing crystals at increasing overall concentration in the crystallizing system. Photoluminescence (PL) spectra were measured to obtain information on defect centers. Emission spectra of all samples showed a narrow UV peak and a broad band in the green-yellow spectral region. The former emission is attributed to exciton recombination, whereas the latter seems to be related with deep-level donors. Latex appears to be a quencher of the visible emission of zinc oxide. Thus, compared to pure zincite, ZnO–latex hybrid materials show a significantly lower PL intensity in the visible range of the spectrum. Under continuous photoexcitation, a noticeable dynamic behavior of the PL is observed, which can be related to a photodesorption of adsorbed oxygen. These surface-adsorbed oxygen species seem to play a crucial role for the optical properties of the materials and may mediate the tunneling of electrons from the conduction band to preexisting deep-level traps, probably related to intrinsic defects (oxygen vacancies or interstitial zinc). The polymer particles can block the sites where oxygen adsorbs, and the disappearance of the “electron-shuttle” species leads to the observed quenching of the visible emission. Electron paramagnetic resonance (EPR) provided additional information about crystal defects with unpaired electrons. Spectra of all samples exhibit a single signal at g ≈ 1.96, typical for shallow donors. Contrary to the results of other authors, no correlation was possible between the EPR signal and the visible range of PL spectra, which suggests that centers responsible for the visible emission and the EPR signal are different.

Synthesis and surface modification of semiconductor nanocrystals

The last decade has witnessed an exponential growth of activities in the field of nanoscience and nanotechnology worldwide, driven both by the excitement of understanding new science and by the potential hope for applications and economic impacts. The largest activity in this field up to date has been in the synthesis and characterization of new materials consisting of particles with dimensions in the order of a few nanometers, so-called nanocrystalline materials. [1-8] Semiconductor nanomaterials such as III/V or II/VI compound semiconductors exhibit strong quantum confinement behavior in the size range from 1 to 10 nm. Therefore, preparation of high quality semiconductor nanocrystals has been a challenge for synthetic chemists, leading to the recent rapid progress in delivering a wide variety of semiconducting nanomaterials. Semiconductor nanocrystals, also called quantum dots, possess physical properties distinctly different from those of the bulk material. Typically, in the size range from 1 to 10 nm, when the particle size is changed, the band gap between the valence and the conduction band will change, too. In a simple approximation a particle in a box model has been used to describe the phenomenon[9]: at nanoscale dimensions the degenerate energy states of a semiconductor separate into discrete states and the system behaves like one big molecule. The size-dependent transformation of the energy levels of the particles is called “quantum size-effect”. Quantum confinement of both the electron and hole in all three dimensions leads to an increase in the effective bandgap of the material with decreasing crystallite size. Consequently, both the optical absorption and emission of semiconductor nanaocrystals shift to the blue (higher energies) as the size of the particles gets smaller. This color tuning is well documented for CdSe nanocrystals whose absorption and emission covers almost the whole visible spectral range. As particle sizes become smaller the ratio of surface atoms to those in the interior increases, which has a strong impact on particle properties, too. Prominent examples are the low melting point [8] and size/shape dependent pressure resistance [10] of semiconductor nanocrystals. Given the size dependence of particle properties, chemists and material scientists now have the unique opportunity to change the electronic and chemical properties of a material by simply controlling the particle size. In particular, CdSe nanocrystals have been widely investigated. Mainly due to their size-dependent optoelectronic properties [11, 12] and flexible chemical processibility [13], they have played a distinguished role for a number of seminal studies [11, 12, 14, 15]. Potential technical applications have been discussed, too. [8, 16-27] Improvement of the optoelectronic properties of semiconductor nanocrystals is still a prominent research topic. One of the most important approaches is fabricating composite type-I core-shell structures which exhibit improved properties, making them attractive from both a fundamental and a practical point of view. Overcoating of nanocrystallites with higher band gap inorganic materials has been shown to increase the photoluminescence quantum yields by eliminating surface nonradiative recombination sites. [28] Particles passivated with inorganic shells are more robust than nanocrystals covered by organic ligands only and have greater tolerance to processing conditions necessary for incorporation into solid state structures or for other applications. Some examples of core-shell nanocrystals reported earlier include CdS on CdSe [29], CdSe on CdS, [30], ZnS on CdS, [31] ZnS on CdSe[28, 32], ZnSe on CdSe [33] and CdS/HgS/CdS [34]. The characterization and preparation of a new core-shell structure, CdSe nanocrystals overcoated by different shells (CdS, ZnS), is presented in chapter 4. Type-I core-shell structures as mentioned above greatly improve the photoluminescence quantum yield and chemical and photochemical stability of nanocrystals. The emission wavelengths of type-I core/shell nanocrystals typically only shows a small red-shift when compared to the plain core nanocrystals. [30, 31, 35] In contrast to type-I core-shell nanocrystals, only few studies have been conducted on colloidal type-II core/shell structures [36-38] which are characterized by a staggered alignment of conduction and valence bands giving rise to a broad tunability of absorption and emission wavelengths, as was shown for CdTe/CdSe core-shell nanocrystals. [36] The emission of type-II core/shell nanocrystals mainly originates from the radiative recombination of electron-hole pairs across the core-shell interface leading to a long photoluminescence lifetime. Type-II core/shell nanocrystals are promising with respect to photoconduction or photovoltaic applications as has been discussed in the literature.[39] Novel type-II core-shell structures with ZnTe cores are reported in chapter 5. The recent progress in the shape control of semiconductor nanocrystals opens new fields of applications. For instance, rod shaped CdSe nanocrystals can enhance the photo-electro conversion efficiency of photovoltaic cells, [40, 41] and also allow for polarized emission in light emitting diodes. [42, 43] Shape control of anisotropic nanocrystals can be achieved by the use of surfactants, [44, 45] regular or inverse micelles as regulating agents, [46, 47] electrochemical processes, [48] template-assisted [49, 50] and solution-liquid-solution (SLS) growth mechnism. [51-53] Recently, formation of various CdSe nanocrystal shapes has been reported by the groups of Alivisatos [54] and Peng, [55] respectively. Furthermore, it has been reported by the group of Prasad [56] that noble metal nanoparticles can induce anisotropic growth of CdSe nanocrystals at lower temperatures than typically used in other methods for preparing anisotropic CdSe structures. Although several approaches for anisotropic crystal growth have been reported by now, developing new synthetic methods for the shape control of colloidal semiconductor nanocrystals remains an important goal. Accordingly, we have attempted to utilize a crystal phase control approach for the controllable synthesis of colloidal ZnE/CdSe (E = S, Se, Te) heterostructures in a variety of morphologies. The complex heterostructures obtained are presented in chapter 6. The unique optical properties of nanocrystals make them appealing as in vivo and in vitro fluorophores in a variety of biological and chemical investigations, in which traditional fluorescence labels based on organic molecules fall short of providing long-term stability and simultaneous detection of multiple emission colours [References]. The ability to prepare water soluble nanocrystals with high stability and quantum yield has led to promising applications in cellular labeling, [57, 58] deep-tissue imaging, [59, 60] and assay labeling [61, 62]. Furthermore, appropriately solubilized nanocrystals have been used as donors in fluorescence resonance energy transfer (FRET) couples. [63-65] Despite recent progress, much work still needs to be done to achieve reproducible and robust surface functionalization and develop flexible (bio-) conjugation techniques. Based on multi-shell CdSe nanocrystals, several new solubilization and ligand exchange protocols have been developed which are presented in chapter 7. The organization of this thesis is as follows: A short overview describing synthesis and properties of CdSe nanocrystals is given in chapter 2. Chapter 3 is the experimental part providing some background information about the optical and analytical methods used in this thesis. The following chapters report the results of this work: synthesis and characterization of type-I multi-shell and type-II core/shell nanocrystals are described in chapter 4 and chapter 5, respectively. In chapter 6, a high–yield synthesis of various CdSe architectures by crystal phase control is reported. Experiments about surface modification of nanocrystals are described in chapter 7. At last, a short summary of the results is given in chapter 8.

Noble-metal nanoparticles produced with colloidal lithography: fabrication, optical properties and applications

In this work, metal nanoparticles produced by nanosphere lithography were studied in terms of their optical properties (in connection to their plasmon resonances), their potential application in sensing platforms - for thin layer sensing and bio-recognition events -, and for a particular case (the nanocrescents), for enhanced spectroscopy studies. The general preparation procedures introduced early in 2005 by Shumaker-Parry et al. to produce metallic nanocrescents were extended to give rise to more complex (isolated) structures, and also, by combining colloidal monolayer fabrication and plasma etching techniques, to arrays of them. The fabrication methods presented in this work were extended not only to new shapes or arrangements of particles, but included also a targeted surface tailoring of the substrates and the structures, using different thiol and silane compounds as linkers for further attachment of, i.e. polyelectrolyte layers, which allow for a controlled tailoring of their nanoenvironment. The optical properties of the nanocrescents were studied with conventional transmission spectroscopy; a simple multipole model was adapted to explain their behaviour qualitatively. In terms of applications, the results on thin film sensing using these particles show that the crescents present an interesting mode-dependent sensitivity and spatial extension. Parallel to this, the penetrations depths were modeled with two simplified schemes, obtaining good agreement with theory. The multiple modes of the particles with their characteristic decay lengths and sensitivities represent a major improvement for particle-sensing platforms compared to previous single resonance systems. The nanocrescents were also used to alter the emission properties of fluorophores placed close to them. In this work, green emitting dyes were placed at controlled distances from the structures and excited using a pulsed laser emitting in the near infrared. The fluorescence signal obtained in this manner should be connected to a two-photon processes triggered by these structures; obtaining first insight into plasmon-mediated enhancement phenomena. An even simpler and faster approach to produce plasmonic structures than that for the crescents was tested. Metallic nanodiscs and nanoellipses were produced by means of nanosphere lithography, extending a procedure reported in the literature to new shapes and optical properties. The optical properties of these particles were characterized by extinction spectroscopy and compared to results from the literature. Their major advantage is that they present a polarization-dependent response, like the nanocrescents, but are much simpler to fabricate, and the resonances can be tailored in the visible with relative ease. The sensing capabilities of the metallic nanodiscs were explored in the same manner as for the nanocrescents, meaning their response to thin layers and to bio-recognition events on their surface. The sensitivity of these nanostructures to thin films proved to be lower than that of the crescents, though in the same order of magnitude. Experimental information about the near field extension for the Au nanodiscs of different sizes was also extracted from these measurements. Further resonance-tailoring approaches based on electrochemical deposition of metals on the nanodiscs were explored, as a means of modifying plasmon resonances by changing surface properties of the nanoparticles. First results on these experiments would indicate that the deposition of Ag on Au on a submonolayer coverage level can lead to important blue-shifts in the resonances, which would open a simple way to tailor resonances by changing material properties in a local manner.

Individual plasmonic nanogaps : controlled assembly and detailed investigation

Diese Arbeit befasst sich mit den optischen Resonanzen metallischer Nanopartikel im Abstand weniger Nanometer von einer metallischen Grenzfläche. Die elektromagnetische Wechselwirkung dieser „Kugel-vor-Fläche“ Geometrie ruft interessante optische Phänomene hervor. Sie erzeugt eine spezielle elektromagnetische Eigenmode, auch Spaltmode genannt, die im Wesentlichen auf den Nanospalt zwi-schen Kugel und Oberfläche lokalisiert ist. In der quasistatischen Näherung hängt die Resonanzposition nur vom Material, der Umgebung, dem Film-Kugel Abstand und dem Kugelradius selbst ab. Theoretische Berechnungen sagen für diese Region unter Resonanzbedingungen eine große Verstärkung des elektro-magnetischen Feldes voraus. rnUm die optischen Eigenschaften dieser Systeme zu untersuchen, wurde ein effizienter plasmonenver-mittelnder Dunkelfeldmodus für die konfokale Rastermikroskopie durch dünne Metallfilme entwickelt, der die Verstärkung durch Oberflächenplasmonen sowohl im Anregungs- als auch Emissionsprozess ausnutzt. Dadurch sind hochwertige Dunkelfeldaufnahmen durch die Metallfilme der Kugel-vor-Fläche Systeme garantiert, und die Spektroskopie einzelner Resonatoren wird erleichtert. Die optischen Untersuchungen werden durch eine Kombination von Rasterkraft- und Rasterelektronenmikroskopie vervollständigt, so dass die Form und Größe der untersuchten Resonatoren in allen drei Dimensionen bestimmt und mit den optischen Resonanzen korreliert werden können. Die Leistungsfähigkeit des neu entwickelten Modus wird für ein Referenzsystem aus Polystyrol-Kugeln auf einem Goldfilm demonstriert. Hierbei zeigen Partikel gleicher Größe auch die erwartete identische Resonanz.rnFür ein aus Gold bestehendes Kugel-vor-Fläche System, bei dem der Spalt durch eine selbstorganisierte Monolage von 2-Aminoethanthiol erzeugt wird, werden die Resonanzen von Goldpartikeln, die durch Reduktion mit Chlorgoldsäure erzeugt wurden, mit denen von idealen Goldkugeln verglichen. Diese ent-stehen aus den herkömmlichen Goldpartikeln durch zusätzliche Bestrahlung mit einem Pikosekunden Nd:Yag Laser. Bei den unbestrahlten Partikeln mit ihrer Unzahl an verschiedenen Formen zeigen nur ein Drittel der untersuchten Resonatoren ein Verhalten, das von der Theorie vorhergesagt wird, ohne das dies mit ihrer Form oder Größe korrelieren würde. Im Fall der bestrahlten Goldkugeln tritt eine spürbare Verbesserung ein, bei dem alle Resonatoren mit den theoretischen Rechnungen übereinstimmen. Eine Änderung der Oberflächenrauheit des Films zeigt hingegen keinen Einfluß auf die Resonanzen. Obwohl durch die Kombination von Goldkugeln und sehr glatten Metallfilmen eine sehr definierte Probengeometrie geschaffen wurde, sind die experimentell bestimmten Linienbreiten der Resonanzen immer noch wesentlich größer als die berechneten. Die Streuung der Daten, selbst für diese Proben, deutet auf weitere Faktoren hin, die die Spaltmoden beeinflußen, wie z.B. die genaue Form des Spalts. rnDie mit den Nanospalten verbundenen hohen Feldverstärkungen werden untersucht, indem ein mit Farbstoff beladenes Polyphenylen-Dendrimer in den Spalt eines aus Silber bestehenden Kugel-vor-Fläche Systems gebracht wird. Das Dendrimer in der Schale besteht lediglich aus Phenyl-Phenyl Bindungen und garantiert durch die damit einhergende Starrheit des Moleküls eine überragende Formstabiliät, ohne gleichzeitig optisch aktiv zu sein. Die 16 Dithiolan Endgruppen sorgen gleichzeitig für die notwendige Affinität zum Silber. Dadurch kann der im Inneren befindliche Farbstoff mit einer Präzision von wenigen Nanometern im Spalt zwischen den Metallstrukturen platziert werden. Der gewählte Perylen Farbstoff zeichnet sich wiederum durch hohe Photostabilität und Fluoreszenz-Quantenausbeute aus. Für alle untersuchten Partikel wird ein starkes Fluoreszenzsignal gefunden, das mindestens 1000-mal stärker ist, als das des mit Farbstoff überzogenen Metallfilms. Das Profil des Fluoreszenz-Anregungsspektrums variiert zwischen den Partikeln und zeigt im Vergleich zum freien Farbstoff eine zusätzliche Emission bei höheren Frequenzen, was in der Literatur als „hot luminescence“ bezeichnet wird. Bei der Untersuchung des Streuverhaltens der Resonatoren können wieder zwei unterschiedliche Arten von Resonatoren un-terschieden werden. Es gibt zunächst die Fälle, die bis auf die beschriebene Linienverbreiterung mit einer idealen Kugel-vor-Fläche Geometrie übereinstimmen und dann andere, die davon stark abweichen. Die Veränderungen der Fluoreszenz-Anregungsspektren für den gebundenen Farbstoffs weisen auf physikalische Mechanismen hin, die bei diesen kleinen Metall/Farbstoff Abständen eine Rolle spielen und die über eine einfache wellenlängenabhängige Verstärkung hinausgehen.

Multifunctional polyether architectures : versatile materials for surface attachment and functionalization

Chapter 1 of this thesis comprises a review of polyether polyamines, i.e., combinations of polyether scaffolds with polymers bearing multiple amino moieties. Focus is laid on controlled or living polymerization methods. Furthermore, fields in which the combination of cationic, complexing, and pH-sensitive properties of the polyamines and biocompatibility and water-solubility of polyethers promise enormous potential are presented. Applications include stimuli-responsive polymers with a lower critical solution temperature (LCST) and/or the ability to gel, preparation of shell cross-linked (SCL) micelles, gene transfection, and surface functionalization.rnIn Chapter 2, multiaminofunctional polyethers relying on the class of glycidyl amine comonomers for anionic ring-opening polymerization (AROP) are presented. In Chapter 2.1, N,N-diethyl glycidyl amine (DEGA) is introduced for copolymerization with ethylene oxide (EO). Copolymer microstructure is assessed using online 1H NMR kinetics, 13C NMR triad sequence analysis, and differential scanning calorimetry (DSC). The concurrent copolymerization of EO and DEGA is found to result in macromolecules with a gradient structure. The LCSTs of the resulting copolymers can be tailored by adjusting DEGA fraction or pH value of the environment. Quaternization of the amino moieties by methylation results in polyelectrolytes. Block copolymers are used for PEGylated gold nanoparticle formation. Chapter 2.2 deals with a glycidyl amine monomer with a removable protecting group at the amino moiety, for liberation of primary amines at the polyether backbone, which is N,N-diallyl glycidyl amine (DAGA). Its allyl groups are able to withstand the harsh basic conditions of AROP, but can be cleaved homogeneously after polymerization. Gradient as well as block copolymers poly(ethylene glycol)-PDAGA (PEG-PDAGA) are obtained. They are analyzed regarding their microstructure, LCST behavior, and cleavage of the protecting groups. rnChapter 3 describes applications of multi(amino)functional polyethers for functionalization of inorganic surfaces. In Chapter 3.1, they are combined with an acetal-protected catechol initiator, leading to well-defined PEG and heteromultifunctional PEG analogues. After deprotection, multifunctional PEG ligands capable of attaching to a variety of metal oxide surfaces are obtained. In a cooperative project with the Department of Inorganic and Analytical Chemistry, JGU Mainz, their potential is demonstrated on MnO nanoparticles, which are promising candidates as T1 contrast agents in magnetic resonance imaging. The MnO nanoparticles are solubilized in aqueous solution upon ligand exchange. In Chapter 3.2, a concept for passivation and functionalization of glass surfaces towards gold nanorods is developed. Quaternized mPEG-b-PqDEGA diblock copolymers are attached to negatively charged glass surfaces via the cationic PqDEGA blocks. The PEG blocks are able to suppress gold nanorod adsorption on the glass in the flow cell, analyzed by dark field microscopy.rnChapter 4 highlights a straightforward approach to poly(ethylene glycol) macrocycles. Starting from commercially available bishydroxy-PEG, cyclic polymers are available by perallylation and ring-closing metathesis in presence of Grubbs’ catalyst. Purification of cyclic PEG is carried out using α-cyclodextrin. This cyclic sugar derivative forms inclusion complexes with remaining unreacted linear PEG in aqueous solution. Simple filtration leads to pure macrocycles, as evidenced by SEC and MALDI-ToF mass spectrometry. Cyclic polymers from biocompatible precursors are interesting materials regarding their increased blood circulation time compared to their linear counterparts.rnIn the Appendix, A.1, a study of the temperature-dependent water-solubility of polyether copolymers is presented. Macroscopic cloud points, determined by turbidimetry, are compared with microscopic aggregation phenomena, monitored by continuous wave electron paramagnetic resonance (CW EPR) spectroscopy in presence of the amphiphilic spin probe and model drug (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). These thermoresponsive polymers are promising candidates for molecular transport applications. The same techniques are applied in Chapter A.2 to explore the pH-dependence of the cloud points of PEG-PDEGA copolymers in further detail. It is shown that the introduction of amino moieties at the PEG backbone allows for precise manipulation of complex phase transition modes. In Chapter A.3, multi-hydroxyfunctional polysilanes are presented. They are obtained via copolymerization of the acetal-protected dichloro(isopropylidene glyceryl propyl ether)methylsilane monomer. The hydroxyl groups are liberated through acidic work-up, yielding versatile access to new multifunctional polysilanes.

The dynamics of ultra-thin polymer films in different confinements studied by resonance enhanced dynamic light scattering

Die Kontroverse über den Glasübergang im Nanometerbereich, z. B. die Glas¬über¬gangs-temperatur Tg von dünnen Polymerfilmen, ist nicht vollständig abgeschlossen. Das dynamische Verhalten auf der Nanoskala ist stark von den einschränkenden Bedingungen abhängig, die auf die Probe wirken. Dünne Polymerfilme sind ideale Systeme um die Dynamik von Polymerketten unter der Einwirkung von Randbedingungen zu untersuchen, wie ich sie in dieser Arbeit variiert habe, um Einblick in dieses Problem zu erhalten.rnrnResonanzverstärkte dynamische Lichtstreuung ist eine Methode, frei von z.B. Fluoreszenzmarkern, die genutzt werden kann um in dünnen Polymerfilmen dynamische Phänomene

Biological applications of plasmonic metal nanoparticles

Plasmons in metal nanoparticles respond to changes in their local environment by a spectral shift in resonance. Here, the potential of plasmonic metal nanoparticles for label-free detection and observation of biological systems is presented. Comparing the material silver and gold concerning plasmonic sensitivity, silver nanoparticles exhibit a higher sensitivity but their chemical instability under light exposure limits general usage. A new approach combining results from optical dark-field microscopy and transmission electron microscopy allows localization and quantification of gold nanoparticles internalized into living cells. Nanorods exposing a negatively charged biocompatible polymer seem to be promising candidates to sense membrane fluctuations of adherent cells. Many small nanoparticles being specific sensing elements can build up a sensor for parallel analyte detection without need of labeling, which is easy to fabricate, re-usable, and has sensitivity down to nanomolar concentrations. Besides analyte detection, binding kinetics of various partner proteins interacting with one protein of interest are accessible in parallel. Gold nanoparticles are able to sense local oscillations in the surface density of proteins on a lipid bilayer, which could not be resolved so far. Studies on the fluorescently labeled system and the unlabeled system identify an influence of the label on the kinetics.

Distensibility and diameter of ascending aorta assessed by cardiac magnetic resonance imaging in adults with tetralogy of fallot or complete transposition

Structural abnormalities of the medial aorta have been described for conotruncal defects (e.g., tetralogy of Fallot [TOF] and complete transposition of the great arteries (dextrotransposition [d]-TGA). In TOF, progressive aortic dilation is a frequent finding. In patients with d-TGA with an atrial switch, this problem is less often described. The aim of the present study was to compare the extent of dilative aortopathy and aortic distensibility in adults with an atrial switch procedure (n = 39) to that in adults with repaired TOF (n = 39) and controls (n = 39), using cardiac magnetic resonance imaging. The groups were matched for age and gender. Diameters of the aorta indexed to the body surface area were significantly increased in the patients with d-TGA and TOF compared to that of the controls at the aortic sinus up to the level of the right pulmonary artery. On multivariate testing, the diagnosis of a conotruncal defect (β = 0.260; p = 0.003) and aortic regurgitant fraction (β = 0.405; p <0.001) were independent predictors of an increased aortic sinus diameter. Ascending aorta distensibility was significantly reduced in those with d-TGA and TOF compared to controls: 3.6 (interquartile range 1.5 to 4.4) versus 2.8 (interquartile range 2.0 to 3.7) versus 5.5 (interquartile range 4.8 to 6.9) ×10(-3) mm Hg(-1) (p <0.001). The independent predictors of ascending aorta distensibility were the diagnosis of a conotruncal defect (p <0.001) and age (p = 0.028). In conclusion, intrinsic aortopathy, manifested as increased ascending aortic diameters and reduced ascending aortic distensibility, is not only evident in adults with TOF, but also in adults with d-TGA and an atrial switch procedure. Long-term follow-up is needed to monitor the aortic size in both patient groups.

Resonance frequency analysis in relation to jawbone characteristics and during early healing of implant installation

OBJECTIVES: To monitor resonance frequency analysis (RFA) in relation to the jawbone characteristics and during the early phases of healing and incorporation of Straumann dental implants with an SLA surface. MATERIAL AND METHODS: 17 Straumann 4.1 mm implants (10 mm) and 7 Straumann 4.8 mm implants (10 mm) were installed and ISQ determined at baseline and after 1, 2, 3, 4, 5, 6, 8 and 12 weeks. Central bone cores were analyzed from the 4.1 mm implants using micro CT for bone volume density (BVD) and bone trabecular connectivity (BTC). RESULTS: Pocket probing depths ranged from 2-4 mm and bleeding on probing from 5-20%. At baseline, BVD varied between 24% and 65% and BTC between 4.9 and 25.4 for the 4.1 mm implants. Baseline ISQ varied between 55 and 74 with a mean of 61.4. No significant correlations were found between BVD or BTC and ISQ Values. For the 4.8 mm diameter implants baseline ISQ values ranged from 57-70 with a mean of 63.3. Over the healing period ISQ values increased at 1 week and decreased after 2-3 weeks. After 4 weeks ISQ values, again increased slightly, no significant differences were noted over time. One implant (4.1 mm) lost stability at 3 weeks. Its ISQ value had dropped from 68 to 45. However the latter value was determined after the clinical diagnosis of instability. CONCLUSION: ISQ values of 57-70 represented homeostasis and implant stability. However no predictive value for loosing implant stability can be attributed to RFA since the decrease occurred after the fact.

Application of 3D documentation and geometric reconstruction methods in traffic accident analysis: with high resolution surface scanning, radiological MSCT/MRI scanning and real data based animation

The examination of traffic accidents is daily routine in forensic medicine. An important question in the analysis of the victims of traffic accidents, for example in collisions between motor vehicles and pedestrians or cyclists, is the situation of the impact. Apart from forensic medical examinations (external examination and autopsy), three-dimensional technologies and methods are gaining importance in forensic investigations. Besides the post-mortem multi-slice computed tomography (MSCT) and magnetic resonance imaging (MRI) for the documentation and analysis of internal findings, highly precise 3D surface scanning is employed for the documentation of the external body findings and of injury-inflicting instruments. The correlation of injuries of the body to the injury-inflicting object and the accident mechanism are of great importance. The applied methods include documentation of the external and internal body and the involved vehicles and inflicting tools as well as the analysis of the acquired data. The body surface and the accident vehicles with their damages were digitized by 3D surface scanning. For the internal findings of the body, post-mortem MSCT and MRI were used. The analysis included the processing of the obtained data to 3D models, determination of the driving direction of the vehicle, correlation of injuries to the vehicle damages, geometric determination of the impact situation and evaluation of further findings of the accident. In the following article, the benefits of the 3D documentation and computer-assisted, drawn-to-scale 3D comparisons of the relevant injuries with the damages to the vehicle in the analysis of the course of accidents, especially with regard to the impact situation, are shown on two examined cases.

Resonance Frequency Analysis (RFA) during early healing

Objectives: - to monitor resonance frequency analysis (RFA) in relation to the jawbone characteristics during the early phases of healing and incorporation of Straumann® dental implants with an SLA surface. Material and methods: 17 Straumann 4.1mm implants (10mm) and 7 Straumann 4.8mm implants (10mm) were installed and ISQ determined at baseline and after 1, 2, 3, 4, 5, 6, 8 and 12 weeks. Central bone cores were analyzed from the 4.1mm implants using micro CT for bone volume density (BVD) and bone trabecular connectivity (BTC). Results: Pocket probing depths ranged between 2-4mm and bleeding on probing between 5-20%. At baseline, BVD varied between 24 and 65% and BTC between 4.9 and 25.4 for the 4.1mm implants. Baseline ISQ varied between 55 and 74 with a mean of 61.4. No significant correlations were found between BVD or BTC and ISQ Values. For the 4.8mm diameter implants baseline ISQ values ranged from 57 – 70 with a mean of 63.3. Over the healing period ISQ values increased at 1 week and decreased after 2-3 weeks. After 4 weeks ISQ values, again increased slightly, no significant differences were noted over time. One implant (4.1mm) lost stability at 3 weeks. Its ISQ value had dropped from 68 to 45. However the latter value was determined after the clinical diagnosis of instability. Conclusion: ISQ values of 57 – 70 represented homeostasis and implant stability. However no predictive value for loosing implant stability can be attributed to RFA since decease occurred after the fact.

Cerebral correlates of muscle tone fluctuations in restless legs syndrome: A pilot study with combined functional magnetic resonance imaging and anterior tibial muscle electromyography

BACKGROUND: The pathology of restless legs syndrome (RLS) is still not understood. To investigate the pathomechanism of the disorder further we recorded a surface electromyogram (EMG) of the anterior tibial muscle during functional magnetic resonance imaging (fMRI) in patients with idiopathic RLS. METHODS: Seven subjects with moderate to severe RLS were investigated in the present pilot study. Patients were lying supine in the scanner for over 50min and were instructed not to move voluntarily. Sensory leg discomfort (SLD) was evaluated on a 10-point Likert scale. For brain image analysis, an algorithm for the calculation of tonic EMG values was developed. RESULTS: We found a negative correlation of tonic EMG and SLD (p <0.01). This finding provides evidence for the clinical experience that RLS-related subjective leg discomfort increases during muscle relaxation at rest. In the fMRI analysis, the tonic EMG was associated with activation in motor and somatosensory pathways and also in some regions that are not primarily related to motor or somatosensory functions. CONCLUSIONS: By using a newly developed algorithm for the investigation of muscle tone-related changes in cerebral activity, we identified structures that are potentially involved in RLS pathology. Our method, with some modification, may also be suitable for the investigation of phasic muscle activity that occurs during periodic leg movements.

An integrated approach for reconstructing surface models of the proximal femur from sparse input data for surgical navigation

A patient-specific surface model of the proximal femur plays an important role in planning and supporting various computer-assisted surgical procedures including total hip replacement, hip resurfacing, and osteotomy of the proximal femur. The common approach to derive 3D models of the proximal femur is to use imaging techniques such as computed tomography (CT) or magnetic resonance imaging (MRI). However, the high logistic effort, the extra radiation (CT-imaging), and the large quantity of data to be acquired and processed make them less functional. In this paper, we present an integrated approach using a multi-level point distribution model (ML-PDM) to reconstruct a patient-specific model of the proximal femur from intra-operatively available sparse data. Results of experiments performed on dry cadaveric bones using dozens of 3D points are presented, as well as experiments using a limited number of 2D X-ray images, which demonstrate promising accuracy of the present approach.