Techn. Universiẗat, Diss., 2005--Clausthal.

Um den Silicium-α-Effekt "als vergrößerte Reaktivität der Si–OC-Bindung" von α-Silanen der allgemeinen Formel ROSiMe2CH2X verglichen mit den entsprechenden γ-Silanen des Typs ROSiMe2(CH2)3X (R = Me, Et; X = funktionelle Gruppe) besser zu verstehen, wurde im Rahmen dieser Arbeit eine systematische experimentelle Untersuchung der Hydrolyse der genannten Alkoxy¬silane durchgeführt. Um die Abhängigkeit der Hydrolyse von der funktionellen Gruppe X, dem Abstand zwischen dem Silicium-Atom und der funktionellen Gruppe X (CH2 oder (CH2)3, α- oder γ-Silan) und dem pD-Wert zu untersuchen, wurde eine Vielzahl an kinetischer Hydrolyse-Studien in CD3CN/D2O unter selbsteinstellendem pD-Wert, unter Verwendung von Pufferlösungen und unter definierten basischen und sauren Bedingungen durchgeführt. Die Kinetik der Hydrolyse der untersuchten Silane wurde dabei mittels 1H-NMR Spektroskopie verfolgt. Die Ergebnisse dieser Untersuchungen zeigen eindeutig, dass der Silicium-α-Effekt nicht als ein einziger Effekt der funktionellen Gruppen verstanden werden kann. Im Gegenteil, die verschiedenen beobachteten Reaktivitäten sind das Resultat mehrerer verschiedener Teileffekte. Die jeweils beobachtete Reaktivität entspricht der Summe der möglichen Teileffekte und kann nicht durch einen bestimmten Silicium-α-Effekt erklärt werden. / To understand the silicon α effect in terms of an enhanced reactivity of the Si–OC bond of α-silanes of the formula type ROSiMe2CH2X compared to analogous γ silanes ROSiMe2(CH2)3X (R = Me, Et; X = functional group), a systematic experimental study of the kinetics and mechanisms of hydrolysis of such compounds was performed. For this purpose, a series of suitable model compounds was synthesized and studied for their hydrolysis kinetics in CD3CN/D2O under basic and acidic conditions, using 1H NMR spectroscopy as the analytical tool. These investigations demonstrated that the silicon α-effect cannot be rationalized in terms of a special single effect. The reactivities observed rather result from a summation of different components, such as electronic and steric effects, pD dependence, and hydrogen bonds between the functional group (or even protonated functional group) and the alkoxy leaving group.

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There are several studies in order to control drug delivery, decrease the toxicity of drugs and also for novel biomedical applications. It is necessary to be able to control the release of the drug within the body by using drug delivery systems. Mesoporous silica compounds have only been discovered twenty years ago and they have already attracted many researchers to study these materials for several applications. SBA-15 particles have a highly ordered regular structure and are a good matrix for guest-host applications. The aim of this study is to be able to address whether the surface functionalization of SBA-15 samples would improve the loading of a drug into these particles. The synthesized SBA-15 particles were surface functionalized by post - grafting synthesis method in order to be used as carrier materials for drug delivery. Amoxicillin was used as a model drug. These mesoporous materials have been characterized using X-ray diffraction (XRD), small-angle X-ray spectroscopy (SAXS), fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), N2 adsorption/ desorption, solid-state silicon nuclear magnetic resonance (Si-NMR), high-performance liquid chromatography (HPLC), ultra-violet (UV) spectroscopy, elemental and thermo gravimetric analysis (TGA). The effect of concentration difference and the type of alkoxysilanes used for the functionalization have been discussed in terms of loading amoxicillin and controlling the delivery. Drug delivery systems have many further applications that still need to be investigated in areas such as neurosciences, cancer and biomedical engineering.

Concrete in its unaltered form allows the mass transfer of fluids into and out of its microstructure. These fluids can contain detrimental solutes which change the chemistry of the cement paste and/or the corrosion properties of the reinforcement bars, most noticeably hydrogen carbonates (HCO3-), oxygen (O2) and chloride ions (Cl-). Water and its solutions containing salts, mostly sodium chloride (NaCl), can also cause physical damage due to phase changes (freezing and thawing).  External application of hydrophobic agents onto the cement paste surface is a well-known method to alter the mass transfer at this interface. Bulk application of hydrophobic agents in ready mixed concrete is also a possible route but alters the entire cement paste. This thesis presents relevant aspects concerning the use of bulk hydrophobic agents in concrete within a spectrum water to cement ratio   (w/c) = 0.40-0.50. The main focus was on triacylglycerides (TAG) and alkyl alkoxysilanes (“silanes”) with application rates 1-3% based on cement weight.  Alterations to the compressive strengths have been observed and documented over a three-year period. The relative drop in mechanical strength is inversely proportional to w/c. The higher the addition rate, the lower the compressive strength. Chemical differences within the hydrophobic groupings (TAG or “silanes”) resulted in different outcomes. This was most noticeable in the water absorption, compressive strengths and chloride diffusion.  Freeze thaw testing did show noticeable differences, the use of “silanes” was detrimental in these tests even in deionsed water. The exact mechanism is unknown, but thin section analysis shows a lack of air entrainer (even when added on the fresh concrete mix) and extensive cracking in the entire cement paste. The scaling in concrete with TAGs was smaller but needs further improving.  The main properties intended with these agents were the ability to alter the mass transfer of water or solutions into the cement paste. Capillary suction and diffusion were examined. Increasing the w/c reduces the effectiveness of the hydrophobic agents to resist water uptake. This was seen in capillary suction and uni-directional chloride diffusion testing. Processed TAGs were more effective in reducing chloride diffusion than the unprocessed chemical whereas, in some cases, the “silanes” actually increased the amount of chloride ions transferred into the cement paste. Only a slight positive effect can be seen at the lower inclusion rate (1%). Increasing the w/c reduces the resistance to chloride ion diffusion with the same dosage rate.  A field test station close to vehicular traffic was also established in 2018 and 2019, but the specimens have not been tested at this point in time. It is hoped that these and other future studies will lead to a complete PhD project. / Betong i sin oförändrade form tillåter masstransport av vätskor i och ur dess mikrostruktur. Dessa vätskor kan innehålla skadliga lösta ämnen som förändrar cementpastans kemi och/eller korrosionsegenskaperna hos armeringsjärnen, framför allt vätekarbonater (HCO3-), syre (O2) och kloridjoner (Cl-). Vatten och dess lösningar som innehåller salter, mestadels natriumklorider (NaCl), kan till och med orsaka fysisk skada på grund av fasförändringar (frysning och upptining). Extern applicering av hydrofoba medel på cementpastans yta är en välkänd metod för att ändra masstransport genom denna gränsyta. Bulkapplicering av hydrofoba medel i färdigblandad betong är också en möjlig väg, och resulterar i förändringar i hela cementpastan. Denna licentiatavhandling presenterar relevanta aspekter rörande användningen av bulk-hydrofoba medel i betong inom intervall av vattencementtal = 0,40-0,50 (vct). Huvudfokus låg på triacylglyceroler (TAG) och alkyl-alkoxisilaner (”silaner”) med inblandning 1-3 % baserat på cementvikt. Förändringar av tryckhållfasthet har observerats och dokumenterats under en treårsperiod. Den relativa reduktionen i mekanisk hållfasthet är omvänt proportionell mot vct. Ju högre tillsatsmängd i cementpastan desto lägre tryckhållfasthet. Kemiska skillnader inom de hydrofoba grupperna (TAG eller "silaner") resulterade i olika resultat. Detta var mest märkbart i vattenabsorption, tryckhållfasthet och kloriddiffusion. Frysprovning visade märkbara skillnader, användningen av "silaner" var skadlig i dessa tester även i avjoniserat vatten. Den exakta mekanismen är okänd, men tunnslipsanalys visar på brist på luftporbildare (även om den tillsätts i stora mängder i den färska betongblandningen) och omfattande sprickbildning i hela cementpastan. Avskalningen i betong med TAG var mindre men behöver ytterligare förbättras. De huvudsakliga egenskaperna avsedda med dessa medel var förmågan att förändra masstransport av vatten eller lösningar till cementpastan. Kapillärsugning och diffusion undersöktes. Att öka vct minskar effektiviteten hos de hydrofoba medlen för att motstå vattenupptagning. Detta sågs vid kapillärsugning och enkelriktad kloriddiffusionsprovning. Raffinerade TAG:er var effektivare att minska kloriddiffusion än den oraffinerade, medan "silanerna" i visa fall faktiskt ökade mängden kloridjoner som överfördes inne i cementpastan. Något positiva effekt kan ses vid den lägre inkluderingstillsatsen (1 %). Att öka vct minskar motståndet mot kloridjondiffusion. En fältteststation intill fordonstrafik etablerades också 2018 och 2019 men provkropparna har inte testats vid denna tidpunkt. Förhoppningen är att dessa och andra framtida studier ska leda till ett komplett doktorandprojekt. / <p>QC 230330</p>