Metachronic malignant transformation of small bowel and rectal endometriosis in the same patient

[ES] Background: Malignant transformation of intestinal endometriosis is a rare event with an unknown rate of incidence. Metachronous progression of endometriosis to adenocarcinoma from two distant intestinal foci happening in the same patient has not been previously reported. Case presentation: We describe a case of metachronic transformation of ileal and rectal endometriosis into an adenocarcinoma occurring in a 45-year-old female without macroscopic pelvic involvement of her endometriosis. First, a right colectomy was performed due to intestinal obstruction by an ileal mass. Pathological examination revealed an ileal endometrioid adenocarcinoma and contiguous microscopic endometriotic foci. Twenty months later, a rectal mass was discovered. An endoscopic biopsy revealed an adenocarcinoma. En bloc anterior rectum resection, hysterectomy and bilateral salpingectomy were performed. A second endometrioid adenocarcinoma arising from a focus of endometriosis within the wall of the rectum was diagnosed. Conclusion: Intestinal endometriosis should be considered a premalignant condition in premenopausal women.

Reproductive biology of Boops boops (Linnaeus, 1758) off Gran Canaria (Canary Islands): a preliminary study

[EN] Preliminary data of the length-weight relationship and reproduction of the bogue Boops boops off Gran Canaria (Canary Islands, Central-east Atlantic) are provided. Two thousand and twenty-one individuals of bogue, ranging from 4 to 34 cm TL, were obtained from purse seine commercial landing. Reproduction parameters as sex determination, duration of spawning season, size at first maturity and GSI variation along time were determinated based on macroscopic evaluation of gonads. The results obtained suggest that bogue is a total spawner, with a long spawning season extending from January to May. Size at first maturity was 16.7 and 17.9 cm TL for males and females, respectively. The length-weight relationship obtained showed a positive allometry in both sexes

Effetti del chitosano su composti polifenolici in colture cellulari di vite: aspetti molecolari e metabolici

Polyphenols, including flavonoids and stilbenes, are an essential part of human diet and constitute one of the most abundant and ubiquitous group of plant secondary metabolites. The level of these compounds is inducible by stress or fungal attack, so attempts are being made to identify likely biotic and abiotic elicitors and to better understand the underlying mechanism. Resveratrol (3,5,4’-trihydroxystilbene), which belongs to the stilbene family, is a naturally occurring polyphenol, found in several fruits, vegetables and beverages including red wine. It is one of the most important plant polyphenols with proved benefic activity on animal health. In the last two decades, the potential protective effects of resveratrol against cardiovascular and neurodegenerative diseases, as well as the chemopreventive properties against cancer, have been largely investigated. The most important source of polyphenols and in particular resveratrol for human diet is grape (Vitis vinifera). Since stilbenes and flavonoids play a very important role in plant defence responses and enviromental interactions, and their effects on human health seem promising, the aim of the research of this Thesis was to study at different levels the activation and the regulation of their biosynthetic pathways after chitosan treatment. Moreover, the polyphenol production in grape cells and the optimisation of cultural conditions bioreactor scale-up, were also investigated. Cell suspensions were obtained from cv. Barbera (Vitis vinifera L.) petioles and were treated with a biotic elicitor, chitosan (50 μg/mL, dissolved in acetic acid) to promote phenylpropanoid metabolism. Chitosan is a D-glucosamine polymer from fungi cell wall and therefore mimes fungal pathogen attack. Liquid cultures have been monitored for 15 days, measuring cell number, cell viability, pH and grams of fresh weight. The endogenous and released amounts of 7 stilbenes (trans and cis isomers of resveratrol, piceid and resveratroloside, and piceatannol), gallic acid, 6 hydroxycinnamic acids (trans-cinnamic, p-coumaric, caffeic, ferulic, sinapic and chlorogenic acids), 5 catechines (catechin, epicatechin, epigallocatechin-gallate (EGCG), epigallocatechin and epicatechin-gallate) and other 5 flavonoids (chalcon, naringenin, kaempferol, quercetin and rutin) in cells and cultural medium, were measured by HPLC-DAD analysis and total anthocyanins were quantified by spectrophotometric analysis. Chitosan was effective in stimulating trans-resveratrol endogenous accumulation with a sharp peak at day 4 (exceeding acetic acid and water controls by 36% and 63%, respectively), while it did not influence the production of the cis-isomer. Compared to both water and acetic acid controls, chitosan decreased the release of both trans- and cis-resveratrol respect to controls. No effect was shown on the accumulation of single resveratrol mono-glucoside isomers, but considering their total amount, normalized for the relative water control, it was possible to evidence an increase in both accumulation and release of those compounds, in chitosan-treated cells, throughout the culture period and particularly during the second week. Many of the analysed flavonoids and hydroxycinnamic acids were not present or detectable in trace amounts. Catechin, epicatechin and epigallocatechin-gallate (EGCG) were detectable both inside the cells and in the culture media, but chitosan did not affect their amounts. On the contrary, total anthocyanins have been stimulated by chitosan and their level, from day 4 to 14, was about 2-fold higher than in both controls, confirming macroscopic observations that treated suspensions showed an intense brown-red color, from day 3 onwards. These elicitation results suggest that chitosan selectively up-regulates specific biosynthetic pathways, without modifying the general accumulation pattern of other flavonoids. Proteins have been extracted from cells at day 4 of culture (corresponding to the production peak of trans-resveratrol) and separated by bidimensional electrophoresis. The 73 proteins that showed a consistently changed amount between untreated, chitosan and acetic acid (chitosan solvent) treated cells, have been identified by mass spectrometry. Chitosan induced an increase in stilbene synthase (STS, the resveratrol biosynthetic enzyme), chalcone-flavanone isomerase (CHI, that switches the pathway from chalcones to flavones and anthocyanins), pathogenesis-related proteins 10 (PRs10, a large family of defence proteins), and a decrease in many proteins belonging to primary metabolisms. A train of six distinct spots of STS encoded by the same gene and increased by chitosan, was detected on the 2-D gels, and related to the different phosphorylation degree of STS spots. Northern blot analyses have been performed on RNA extracted from cells treated with chitosan and relative controls, using probes for STS, PAL (phenylalanine ammonia lyase, the first enzyme of the biosynthetic pathway), CHS (chalcone synthase, that shares with STS the same precursors), CHI and PR-10. The up-regulation of PAL, CHS and CHI transcript expression levels correlated with the accumulation of anthocyanins. The strong increase of different molecular weight PR-10 mRNAs, correlated with the 11 PR-10 protein spots identified in proteomic analyses. The sudden decrease in trans-resveratrol endogenous accumulation after day 4 of culture, could be simply explained by the diminished resveratrol biosynthetic activity due to the lower amount of biosynthetic enzymes. This might be indirectly demonstrated by northern blot expression analyses, that showed lower levels of phenylalanine ammonia lyase (PAL) and stilbene synthase (STS) mRNAs starting from day 4. Other possible explanations could be a resveratrol oxidation process and/or the formation of other different mono-, di-glucosides and resveratrol oligomers such as viniferins. Immunolocalisation experiments performed on grape protoplasts and the subsequent analyses by confocal microscope, showed that STS, and therefore the resveratrol synthetic site, is mostly associated to intracellular membranes close to the cytosolic side of plasma membrane and in a smaller amount is localized in the cytosol. STS seemed not to be present inside vacuole and nucleus. There were no differences in the STS intracellular localisation between the different treatments. Since it was shown that stilbenes are largely released in the culture medium and that STS is a soluble protein, a possible interaction of STS with a plasma membrane transporter responsible for the extrusion of stilbenes in the culture medium, might be hypothesized. Proteomic analyses performed on subcellular fractions identified in the microsomial fraction 5 proteins taking part in channel complexes or associated with channels, that significantly changed their amount after chitosan treatment. In soluble and membrane fractions respectively 3 and 4 STS and 6 and 3 PR-10 have been identified. Proteomic results obtained from subcellular fractions substantially confirmed previous result obtained from total cell protein extracts and added more information about protein localisation and co-localisation. The interesting results obtained on Barbera cell cultures with the aim to increase polyphenol (especially stilbenes) production, have encouraged scale up tests in 1 litre bioreactors. The first trial fermentation was performed in parallel with a normal time-course in 20 mL flasks, showing that the scale-up (bigger volume and different conditions) process influenced in a very relevant way stilbenes production. In order to optimise culture parameters such as medium sucrose amount, fermentation length and inoculum cell concentration, few other fermentations were performed. Chitosan treatments were also performed. The modification of each parameter brought relevant variations in stilbenes and catechins levels, so that the production of a certain compound (or class of compounds) could be hypothetically promoted by modulating one or more culture parameters. For example the catechin yield could be improved by increasing sucrose content and the time of fermentation. The best results in stilbene yield were obtained in a 800 mL fermentation inoculated with 10.8 grams of cells and supplemented with chitosan. The culture was fed with MS medium added with 30 g/L sucrose, 25 μg/mL rifampicin and 50 μg/mL of chitosan, and was maintained at 24°C, stirred by marine impeller at 100 rpm and supplied of air at 0.16 L/min rate. Resveratroloside was the stilbene present in the larger amount, 3-5 times more than resveratrol. Because resveratrol glucosides are similarly active and more stable than free resveratrol, their production using a bioreactor could be a great advantage in an hypothetical industrial process. In my bioreactor tests, stilbenes were mainly released in the culture medium (60-80% of the total) and this fact could be another advantage for industrial applications, because it allows recovering the products directly from the culture medium without stopping the fermentation and/or killing the cells. In my best cultural conditions, it was possible to obtain 3.95 mg/L of stilbenes at day 4 (maximum resveratrol accumulation) and 5.13 mg/L at day 14 (maximum resveratroloside production). In conclusion, chitosan effect in inducing Vitis vinifera defense mechanisms can be related to its ability to increase the intracellular content of a large spectrum of antioxidants, and in particular of resveratrol, its derivates and anthocyanins. Its effect can be observed at transcriptional, proteomic (variation of soluble and membrane protein amounts) and metabolic (polyphenols production) level. The chitosan ability to elicit specific plant matabolisms can be useful to produce large quantities of antioxidant compounds from cell culture in bioreactor.

L'infiammazione intestinale nell'animale sperimentale come modello per lo sviluppo di nuovi farmaci: ruolo della via tachichininergica nelle malattie infiammatorie intestinali

Background: Several lines of evidence showed that inflammation is associated with changes in the expression of tachykinins both in human and animal models. Tachykinins, including substance P (SP), are small peptides expressed in the extrinsic primary afferent nerve fibres and enteric neurons of the gut: they exert their action through three distinct receptors, termed NK1, NK2 and NK3. SP modulates intestinal motility and enteric secretion, acting preferentially through the NK1 receptor. SP neural network and NK1 receptor expression are increased in patients with inflammatory bowel disease, and similar changes were observed in experimental models of inflammation. The 2,4 Dinitrobenzene Sulphonic Acid (DNBS) model of colitis is useful to study innate immunity, non-specific inflammation and wound healing; it has been suggested that the transmural inflammation seen in this model resembles that found in Crohn’s disease and can therefore be used to study what cells and mediators are involved in this type of inflammation. Aim: To test the possible protective effect of the NK1 receptor antagonist SSR140333 on: 1) acute model of intestinal inflammation; 2) reactivation of DNBS-induced colitis in rats. Methods: Acute colitis was induced in male SD rats by intrarectal administration of DNBS (15 mg/rat in 50% ethanol). Reactivation of colitis was induced by intrarectal injections of DNBS on day 28 (7.5 mg/rat in 35% ethanol). Animals were sacrificed on day 6 (acute colitis) and 29 (reactivation of colitis). SSR140333 (10 mg/kg) was administered orally starting from the day before the induction of colitis for 7 days (acute colitis) or seven days before the reactivation of colitis. Colonic damage was assessed by means of macroscopic and microscopic scores, myeloperoxidase activity (MPO) and TNF-α tissue levels. Enzyme immunoassay was used to measure colonic substance P levels. Statistical analysis was performed using analysis of variance (one-way or two-way, as appropriate) with the Bonferroni’s correction for multiple comparisons. Results: DNBS administration impaired body weight gain and markedly increased all inflammatory parameters (p<0.01). Treatment with SSR140333 10 mg/kg significantly counteracted the impairment in body weight gain, decreased macroscopic and histological scores and reduced colonic myeloperoxidase activity (p<0.01). Drug treatment counteracted TNF-α tissue levels and colonic SP concentrations (acute model). Similar results were obtained administering the NK1 receptor antagonist SSR140333 (3 and 10 mg/kg) for 5 days, starting the day after the induction of colitis. Intrarectal administration of DNBS four weeks after the first DNBS administration resulted in reactivation of colitis, with increases in macroscopic and histological damage scores and increase in MPO activity. Preventive treatment with SSR140333 10 mg/kg decreased macroscopic damage score, significantly reduced microscopic damage score but did not affect MPO activity. Conclusions: Treatment with SSR140333 significantly reduced intestinal damage in acute model of intestinal inflammation in rats. The NK1 receptor antagonist SSR140333 was also able to prevent relapse in experimental colitis. These results support the hypothesis of SP involvement in intestinal inflammation and indicate that NK receptor antagonists may have a therapeutic potential in inflammatory bowel disease.

Dalla città alla casa, dalla casa alla città: la mutevole ricerca di un Piano per il ben-essere urbano

La ricerca si propone di definire le linee guida per la stesura di un Piano che si occupi di qualità della vita e di benessere. Il richiamo alla qualità e al benessere è positivamente innovativo, in quanto impone agli organi decisionali di sintonizzarsi con la soggettività attiva dei cittadini e, contemporaneamente, rende evidente la necessità di un approccio più ampio e trasversale al tema della città e di una più stretta relazione dei tecnici/esperti con i responsabili degli organismi politicoamministrativi. La ricerca vuole indagare i limiti dell’urbanistica moderna di fronte alla complessità di bisogni e di nuove necessità espresse dalle popolazioni urbane contemporanee. La domanda dei servizi è notevolmente cambiata rispetto a quella degli anni Sessanta, oltre che sul piano quantitativo anche e soprattutto sul piano qualitativo, a causa degli intervenuti cambiamenti sociali che hanno trasformato la città moderna non solo dal punto di vista strutturale ma anche dal punto di vista culturale: l’intermittenza della cittadinanza, per cui le città sono sempre più vissute e godute da cittadini del mondo (turisti e/o visitatori, temporaneamente presenti) e da cittadini diffusi (suburbani, provinciali, metropolitani); la radicale trasformazione della struttura familiare, per cui la famiglia-tipo costituita da una coppia con figli, solido riferimento per l’economia e la politica, è oggi minoritaria; l’irregolarità e flessibilità dei calendari, delle agende e dei ritmi di vita della popolazione attiva; la mobilità sociale, per cui gli individui hanno traiettorie di vita e pratiche quotidiane meno determinate dalle loro origini sociali di quanto avveniva nel passato; l’elevazione del livello di istruzione e quindi l’incremento della domanda di cultura; la crescita della popolazione anziana e la forte individualizzazione sociale hanno generato una domanda di città espressa dalla gente estremamente variegata ed eterogenea, frammentata e volatile, e per alcuni aspetti assolutamente nuova. Accanto a vecchie e consolidate richieste – la città efficiente, funzionale, produttiva, accessibile a tutti – sorgono nuove domande, ideali e bisogni che hanno come oggetto la bellezza, la varietà, la fruibilità, la sicurezza, la capacità di stupire e divertire, la sostenibilità, la ricerca di nuove identità, domande che esprimono il desiderio di vivere e di godere la città, di stare bene in città, domande che non possono essere più soddisfatte attraverso un’idea di welfare semplicemente basata sull’istruzione, la sanità, il sistema pensionistico e l’assistenza sociale. La città moderna ovvero l’idea moderna della città, organizzata solo sui concetti di ordine, regolarità, pulizia, uguaglianza e buon governo, è stata consegnata alla storia passata trasformandosi ora in qualcosa di assai diverso che facciamo fatica a rappresentare, a descrivere, a raccontare. La città contemporanea può essere rappresentata in molteplici modi, sia dal punto di vista urbanistico che dal punto di vista sociale: nella letteratura recente è evidente la difficoltà di definire e di racchiudere entro limiti certi l’oggetto “città” e la mancanza di un convincimento forte nell’interpretazione delle trasformazioni politiche, economiche e sociali che hanno investito la società e il mondo nel secolo scorso. La città contemporanea, al di là degli ambiti amministrativi, delle espansioni territoriali e degli assetti urbanistici, delle infrastrutture, della tecnologia, del funzionalismo e dei mercati globali, è anche luogo delle relazioni umane, rappresentazione dei rapporti tra gli individui e dello spazio urbano in cui queste relazioni si muovono. La città è sia concentrazione fisica di persone e di edifici, ma anche varietà di usi e di gruppi, densità di rapporti sociali; è il luogo in cui avvengono i processi di coesione o di esclusione sociale, luogo delle norme culturali che regolano i comportamenti, dell’identità che si esprime materialmente e simbolicamente nello spazio pubblico della vita cittadina. Per studiare la città contemporanea è necessario utilizzare un approccio nuovo, fatto di contaminazioni e saperi trasversali forniti da altre discipline, come la sociologia e le scienze umane, che pure contribuiscono a costruire l’immagine comunemente percepita della città e del territorio, del paesaggio e dell’ambiente. La rappresentazione del sociale urbano varia in base all’idea di cosa è, in un dato momento storico e in un dato contesto, una situazione di benessere delle persone. L’urbanistica moderna mirava al massimo benessere del singolo e della collettività e a modellarsi sulle “effettive necessità delle persone”: nei vecchi manuali di urbanistica compare come appendice al piano regolatore il “Piano dei servizi”, che comprende i servizi distribuiti sul territorio circostante, una sorta di “piano regolatore sociale”, per evitare quartieri separati per fasce di popolazione o per classi. Nella città contemporanea la globalizzazione, le nuove forme di marginalizzazione e di esclusione, l’avvento della cosiddetta “new economy”, la ridefinizione della base produttiva e del mercato del lavoro urbani sono espressione di una complessità sociale che può essere definita sulla base delle transazioni e gli scambi simbolici piuttosto che sui processi di industrializzazione e di modernizzazione verso cui era orientata la città storica, definita moderna. Tutto ciò costituisce quel complesso di questioni che attualmente viene definito “nuovo welfare”, in contrapposizione a quello essenzialmente basato sull’istruzione, sulla sanità, sul sistema pensionistico e sull’assistenza sociale. La ricerca ha quindi analizzato gli strumenti tradizionali della pianificazione e programmazione territoriale, nella loro dimensione operativa e istituzionale: la destinazione principale di tali strumenti consiste nella classificazione e nella sistemazione dei servizi e dei contenitori urbanistici. E’ chiaro, tuttavia, che per poter rispondere alla molteplice complessità di domande, bisogni e desideri espressi dalla società contemporanea le dotazioni effettive per “fare città” devono necessariamente superare i concetti di “standard” e di “zonizzazione”, che risultano essere troppo rigidi e quindi incapaci di adattarsi all’evoluzione di una domanda crescente di qualità e di servizi e allo stesso tempo inadeguati nella gestione del rapporto tra lo spazio domestico e lo spazio collettivo. In questo senso è rilevante il rapporto tra le tipologie abitative e la morfologia urbana e quindi anche l’ambiente intorno alla casa, che stabilisce il rapporto “dalla casa alla città”, perché è in questa dualità che si definisce il rapporto tra spazi privati e spazi pubblici e si contestualizzano i temi della strada, dei negozi, dei luoghi di incontro, degli accessi. Dopo la convergenza dalla scala urbana alla scala edilizia si passa quindi dalla scala edilizia a quella urbana, dal momento che il criterio del benessere attraversa le diverse scale dello spazio abitabile. Non solo, nei sistemi territoriali in cui si è raggiunto un benessere diffuso ed un alto livello di sviluppo economico è emersa la consapevolezza che il concetto stesso di benessere sia non più legato esclusivamente alla capacità di reddito collettiva e/o individuale: oggi la qualità della vita si misura in termini di qualità ambientale e sociale. Ecco dunque la necessità di uno strumento di conoscenza della città contemporanea, da allegare al Piano, in cui vengano definiti i criteri da osservare nella progettazione dello spazio urbano al fine di determinare la qualità e il benessere dell’ambiente costruito, inteso come benessere generalizzato, nel suo significato di “qualità dello star bene”. E’ evidente che per raggiungere tale livello di qualità e benessere è necessario provvedere al soddisfacimento da una parte degli aspetti macroscopici del funzionamento sociale e del tenore di vita attraverso gli indicatori di reddito, occupazione, povertà, criminalità, abitazione, istruzione, etc.; dall’altra dei bisogni primari, elementari e di base, e di quelli secondari, culturali e quindi mutevoli, trapassando dal welfare state allo star bene o well being personale, alla wellness in senso olistico, tutte espressioni di un desiderio di bellezza mentale e fisica e di un nuovo rapporto del corpo con l’ambiente, quindi manifestazione concreta di un’esigenza di ben-essere individuale e collettivo. Ed è questa esigenza, nuova e difficile, che crea la diffusa sensazione dell’inizio di una nuova stagione urbana, molto più di quanto facciano pensare le stesse modifiche fisiche della città.

Il ruolo dell'ecografia prenatale nell'infezione congenita da Citomegalovirus

OBJECTIVE: To assess the effectiveness of ultrasound in the antenatal prediction of symptomatic congenital cytomegalovirus infection. STUDY DESIGN: The sonograms of 650 fetuses from mothers with primary cytomegalovirus infection were correlated to fetal/neonatal outcome. Infection status was disclosed by viral urine isolation at birth or CMV tissue inclusions at autopsy. Classification of symptomatic disease was based on postnatal clinical/laboratory findings or macroscopic evidence of tissue damage at autopsy. RESULTS: Ultrasound abnormalities were found in 51/600 (8.5%) mothers with primary infection and in 23/154 congenitally infected fetuses (14.9%). Symptomatic congenital infection resulted in 18/23 and 68/131 cases with or without abnormal sonographic findings, respectively. Positive predictive values of ultrasound versus symptomatic congenital infection was 35.3% relating to all fetuses/infants from mothers with primary infection and 78.3% relating to fetuses/infants with congenital infection. CONCLUSION: When fetal infection status is unknown, ultrasound abnormalities only predict symptomatic congenital infection in a third of cases.

Computer simulation of ordering and dynamics in liquid crystals in the bulk and close to the surface

The aim of this PhD thesis is to investigate the orientational and dynamical properties of liquid crystalline systems, at molecular level and using atomistic computer simulations, to reach a better understanding of material behavior from a microscopic point view. In perspective this should allow to clarify the relation between the micro and macroscopic properties with the objective of predicting or confirming experimental results on these systems. In this context, we developed four different lines of work in the thesis. The first one concerns the orientational order and alignment mechanism of rigid solutes of small dimensions dissolved in a nematic phase formed by the 4-pentyl,4 cyanobiphenyl (5CB) nematic liquid crystal. The orientational distribution of solutes have been obtained with Molecular Dynamics Simulation (MD) and have been compared with experimental data reported in literature. we have also verified the agreement between order parameters and dipolar coupling values measured in NMR experiments. The MD determined effective orientational potentials have been compared with the predictions of Maier­Saupe and Surface tensor models. The second line concerns the development of a correct parametrization able to reproduce the phase transition properties of a prototype of the oligothiophene semiconductor family: sexithiophene (T6). T6 forms two crystalline polymorphs largely studied, and possesses liquid crystalline phases still not well characterized, From simulations we detected a phase transition from crystal to liquid crystal at about 580 K, in agreement with available experiments, and in particular we found two LC phases, smectic and nematic. The crystal­smectic transition is associated to a relevant density variation and to strong conformational changes of T6, namely the molecules in the liquid crystal phase easily assume a bent shape, deviating from the planar structure typical of the crystal. The third line explores a new approach for calculating the viscosity in a nematic through a virtual exper- iment resembling the classical falling sphere experiment. The falling sphere is replaced by an hydrogenated silicon nanoparticle of spherical shape suspended in 5CB, and gravity effects are replaced by a constant force applied to the nanoparticle in a selected direction. Once the nanoparticle reaches a constant velocity, the viscosity of the medium can be evaluated using Stokes' law. With this method we successfully reproduced experimental viscosities and viscosity anisotropy for the solvent 5CB. The last line deals with the study of order induction on nematic molecules by an hydrogenated silicon surface. Gaining predicting power for the anchoring behavior of liquid crystals at surfaces will be a very desirable capability, as many properties related to devices depend on molecular organization close to surfaces. Here we studied, by means of atomistic MD simulations, the flat interface between an hydrogenated (001) silicon surface in contact with a sample of 5CB molecules. We found a planar anchoring of the first layers of 5CB where surface interactions are dominating with respect to the mesogen intermolecular interactions. We also analyzed the interface 5CB­vacuum, finding a homeotropic orientation of the nematic at this interface.

Modellierung von Porenraumgeometrien und Transport in korngestützten porösen Medien

Poröse Medien spielen in der Hydrosphäre eine wesentliche Rolle bei der Strömung und beim Transport von Stoffen. In diesem Raum finden komplexe Prozesse statt: Advektion, Kon-vektion, Diffusion, hydromechanische Dispersion, Sorption, Komplexierung, Ionenaustausch und Abbau. Die strömungsmechanischen- und die Transportverhältnisse in porösen Medien werden direkt durch die Geometrie des Porenraumes selbst und durch die Eigenschaften der transportierten (oder strömenden) Medien bestimmt. In der Praxis wird eine Vielzahl von empirischen Modellen verwendet, die die Eigenschaften des porösen Mediums in repräsentativen Elementarvolumen wiedergeben. Die Ermittlung der in empirischen Modellen verwendeten Materialparameter erfolgt über Labor- oder Feldbestimmungsmethoden. Im Rahmen dieser Arbeit wurde das Computer-modell PoreFlow entwickelt, welches die hydraulischen Eigenschaften eines korngestützten porösen Mediums aus der mikroskopischen Modellierung des Fluidflusses und Transportes ableitet. Das poröse Modellmedium wird durch ein dreidimensionales Kugelpackungsmodell, zusam-mengesetzt aus einer beliebigen Kornverteilung, dargestellt. Im Modellporenraum wird die Strömung eines Fluids basierend auf einer stationären Lösung der Navier-Stokes-Gleichung simuliert. Die Ergebnisse der Modellsimulationen an verschiedenen Modellmedien werden mit den Ergebnissen von Säulenversuchen verglichen. Es zeigt sich eine deutliche Abhängigkeit der Strömungs- und Transportparameter von der Porenraumgeometrie sowohl in den Modell-simulationen als auch in den Säulenexperimenten.

Liquid crystal polymer brushes and their application as alignment layers in liquid crystal cells

Liquid Crystal Polymer Brushes and their Application as Alignment Layers in Liquid Crystal Cells Polymer brushes with liquid crystalline (LC) side chains were synthesized on planar glass substrates and their nematic textures were investigated. The LC polymers consist of an acrylate or a methacrylate main chain and a phenyl benzoate group as the mesogenic unit which is connected to the main chain via a flexible alkyl spacer composed of six CH2 units. The preparation of the LC polymer brushes was carried out according to the “grafting from” technique: polymerization is carried out from azo-initiators that have been previously self-assembled on the substrate. LC polymer brushes with a thickness from a few nm to 230 nm were synthesized by varying the monomer concentration and the polymerization time. The LC polymer brushes were thick enough to allow for direct observation of the nematic textures with a polarizing microscope. The LC polymer brushes grown on untreated glass substrates exhibited irregular textures (“polydomains”). The domain size is in the range of some micrometers and depends only weakly on the brush thickness. The investigations on the texture-temperature relationship of the LC brushes revealed that the brushes exhibit a surface memory effect, that is, the identical texture reappears after the LC brush sample has experienced a thermal isotropization or a solvent treatment, at which the nematic LC state has been completely destroyed. The surface memory effect is attributed to a strong anchoring of the orientation of the mesogenic units to heterogeneities at the substrate surface. The exact nature of the surface heterogeneities is unknown. The effect was observed for the LC brushes swollen with low molecular weight nematic molecules, as well. Rubbing the glass substrate with a piece of velvet cloth prior to the surface modification with the initiator and the brush growth gives rise to the formation of homogenous alignment of the mesogenic units in the LC polymer side chains. Monodomain textures were obtained for these LC brushes. The mechanism for the homogeneous alignment is based on the transfer of Nylon fibers during the rubbing process. A surfactant was mixed with the azo-initiator in modifying rubbed substrates for subsequent brush generation. Such brushes exhibited biaxial optical properties. Hybrid LC cells made from a substrate modified with biaxial brushes and a rubbed glass substrate show an orientation with a tilt angle of a = –15.6 . This work shows that LC brushes grown on rubbed surfaces fulfill the important criteria for alignment layers: the formation of macroscopic monodomains. First results indicate that by diluting the brush with molecules which are also covalently bound to the surface but induce a different orientation, a system is obtained in which the two conflicting alignment mechanisms can be used to generate a tilted alignment. In order to allow for an application of the alignment layers into a potential product, subsequent work should focus on the questions how easy and in which range the tilt angle can be controlled.

Control of the long-range self-organization of polycyclic aromatic hydrocarbons for device applications

Electronic devices based on organic semiconductors have gained increased attention in nanotechnology, especially applicable to the field of field-effect transistors and photovoltaic. A promising class of materials in this reseach field are polycyclic aromatic hydrocarbons (PAHs). Alkyl substitution of these graphenes results in the selforganization into one-dimensional columnar superstructures and provides solubility and processibility. The nano-phase separation between the π-stacking aromatic cores and the disordered peripheral alkyl chains leads to the formation of thermotropic mesophases. Hexa-peri-hexabenzocoronenes (HBC), as an example for a PAH, exhibits some of the highest values for the charge carrier mobility for mesogens, which makes them promising candidates for electronic devices. Prerequisites for efficient charge carrier transport between electrodes are a high purity of the material to reduce possible trapping sites for charge carriers and a pronounced and defect-free, long-range order. Appropriate processing techniques are required to induce a high degree of aligned structures in the discotic material over macroscopic dimensions. Highly-ordered supramolecular structures of different discotics, in particular, of HBC derivatives have been obtained by solution processing using the zone-casting technique, zone-melting or simple extrusion. Simplicity and fabrication of highly oriented columnar structures over long-range are the most essential advantages of these zone-processing methods. A close relation between the molecular design, self-aggregation and the processing conditions has been revealed. The long-range order achieved by the zone-casting proved to be suitable for field effect transistors (FET).