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OBJECTIVES: Low- grade inflammation is a pathological feature of a wide range of chronic conditions, including the metabolic syndrome, cardiovascular diseases (CVD)(1, 2) and the accelerated reduction in bone density(3). Previous research shows that diets rich in fruits and vegetables can reduce chronic inflammation(4, 5). To date there is no data on multiyear clinical interventions assessing the effect of plant-based dietary supplements on low-grade inflammation, cardiovascular disease prevention and indicators of biological aging. To assess the long-term effect of two plant based macro- and micronutrient food supplements on low-grade inflammation, cardiovascular disease prevention and indicators of biological ageing in overweight, elderly people. METHODS: This is a 3-arm open labelled, balanced, parallel design, observational study assessing the effectiveness of two different supplements vs control. Ninety overweight and obese volunteers, aged 50–80 years, will be recruited and followed up for the duration of 2 years. Since this is a long term trial and in order to maximize adherence to interventions, we will allow volunteers to choose their preferred treatment and we will implement a propensity score design. More specifically, for each participant an individual score based on certain parameters will be calculated (Table 1) and will be matched with another participant with the same propensity score across the three groups, exerting a ‘post-randomization’ effect. Multiple primary endpoints will be changes in markers of low-grade inflammation, CVD risk and micronutrients status (Table 2). Secondary outcomes will include assessment of Upper Respiratory Tract Symptoms, Gastrointestinal Symptoms, Quality of Life and Anthropometry. Furthermore, Cognitive Function, Bone quality and Leucocyte Telomere length will be assessed as tertiary outcomes. RESULTS: n/a CONCLUSIONS: This study will provide data on the effect of long-term, plant-based supplementation on chronic conditions and nutritional status in aging. In addition, the novel study design implemented might counteract the high dropout rate often observed in long term nutritional interventions and might create a new era with regards to study design approach in the field of nutritional science. FUNDING SOURCES: The Juice Plus+ Science Institute received funding by The Juice Plus+® Company for this project. SUPPORTING TABLES, IMAGES AND/OR GRAPHS

A series of arylsilanetriols [Aryl–Si(OH)3, Aryl = 2,6-dimethylphenyl, 2,4,6-trimethylphenyl 2,3,5,6-tetramethylphenyl] with two, three, and four methyl groups at the phenyl ring was prepared from the corresponding trichlorosilanes. While the durene substituted silanetriol was formed exclusively, the other silanetriols were obtained together with their primary condensation products in a constant ratio 4:1. For the mesityl-substituted derivative an alternative synthetic access via the trialkoxysilane was explored, which turned out to be inferior in terms of product yield. Despite their increased steric size the methylated phenylsilanetriols are prone to condensation in solution as well in the solid state, although the dimerization rate is reduced compared to the unsubstituted phenylsilanetriol. All compounds were characterized with 29Si, 1H, 13C NMR, HRMS elemental analysis, IR spectroscopy, and in some cases single X-ray crystallography.

Small angle X-ray scattering (SAXS) is employed to characterize the inner structure and shape of aqueous nanocrystalline cellulose suspensions using the generalized indirect Fourier transformation (GIFT). The use of the GIFT approach provides a single fitting procedure for the determination of intra- and interparticle interactions due to a simultaneous treatment of the form factor P(q) and the structure factor S(q). Moreover, GIFT allows for the determination of particle charges and polydispersity indices. As test material, aqueous nanocrystalline cellulose suspensions (aNCS) prepared by the H2SO4 route have been investigated and characterized (SAXS, dynamic light scattering, zeta potential).

The adsorption behavior of cellulose-4-[ N -methylammonium]butyrate chloride (CMABC) on two hydrophilic substrates is studied, namely nanometric cellulose model thin films and silicon dioxide substrates. The adsorption is quantified in dependence of electrolyte concentration and pH value using a quartz crystal microbalance with dissipation (QCM-D). In case of CMABC, at high ionic strengths (25–100 mM NaCl) high adsorption is observed at pH 7 (Δ f 3 : −15 to −17 Hz) while at lower ionic strengths (1–10 mM) less CMABC (Δ f 3 : −2 to −12 Hz) is deposited on the cellulose surfaces as indicated by the frequency changes using QCM-D. A change in pH value from 7 to 8 reveals an increase in adsorption. Atomic force microscopy shows that the coating of cellulose thin films with CMABC changes the morphology from a fibrillar to a particle like structure on the surface. The surface wettability with water increases with an increasing amount of CMABC on the surface compared to neat cellulose model films. At lower pH values (3 and 5), CMABC does not adsorb onto the cellulose model thin films. XPS is used to validate the results and to determine the nitrogen content of the surfaces. In addition, adsorption of CMABC onto another hydrophilic and negatively charged substrate, silicon dioxide coated quartz crystals, cannot be detected at different pH values and electrolyte concentrations as proven by QCM-D.

In many areas of science and technology, patterned films and surfaces play a key role in engineering and development of advanced materials. Here, we introduce a new generic technique for the fabrication of polysaccharide nano-structures via focused electron beam induced conversion (FEBIC). For the proof of principle, organosoluble trimethylsilyl-cellulose (TMSC) thin films have been deposited by spin coating on SiO2 / Si and exposed to a nano-sized electron beam. It turns out that in the exposed areas an electron induced desilylation reaction takes place converting soluble TMSC to rather insoluble cellulose. After removal of the unexposed TMSC areas, structured cellulose patterns remain on the surface with FWHM line widths down to 70 nm. Systematic FEBIC parameter sweeps reveal a generally electron dose dependent behavior with three working regimes: incomplete conversion, ideal doses and over exposure. Direct (FT-IR) and indirect chemical analyses (enzymatic degradation) confirmed the cellulosic character of ideally converted areas. These investigations are complemented by a theoretical model which suggests a two-step reaction process by means of TMSC → cellulose and cellulose → non-cellulose material conversion in excellent agreement with experimental data. The extracted, individual reaction rates allowed the derivation of design rules for FEBIC parameters towards highest conversion efficiencies and highest lateral resolution.

In this contribution, we explore the interaction of lignocellulosics and proteins aiming at a better understanding of their synergistic role in natural systems. In particular, the manufacturing and characterization of amphiphilic bicomponent thin films composed of hydrophilic cellulose and a hydrophobic lignin ester in different ratios is presented which may act as a very simplified model for real systems. Besides detailed characterizations of the films and mechanisms to explain their formation, nonspecific protein adsorption using bovine serum albumin (BSA) onto the films was studied using a quartz crystal microbalance with dissipation (QCM-D). As it turns out, the rather low nonspecific protein adsorption of BSA on cellulose is further reduced when these hydrophobic lignins are incorporated into the films. The lignin ester acts in these blend films as sacrificial component, probably via an emulsification mechanism. Additionally, the amphiphilicity of the films may prevent the adsorption of BSA as well. Although there are some indications, it remains unclear whether any kind of protein interactions in such systems are of specific nature.

Two different lithographic techniques for the patterning of thin biopolymer films are developed. The first method is based on using a microstructured elastomeric mold for the structuring of thin films of regenerated cellulose. The thin films are manufactured by spin-coating of trimethylsilyl cellulose (TMSC) and subsequent regeneration. The microchannels formed by the mold and the cellulose film are filled with a cellulase solution by capillary action. In the areas exposed to the enzyme solution, the cellulose film is digested, whereas the area in contact with the mold is protected from the enzymatic activity. Optical thickness measurements, atomic force microscopy and fluorescent staining confirm a successful patterning of cellulose on several substrates by this method. The second method is based on the structured regeneration of thin TMSC films. TMSC surfaces are protected with metal masks and exposed to vapors of hydrochloric acid. These treatments result in hydrophilic cellulose structures surrounded by hydrophobic TMSC with differing physicochemical properties. Treatments of the obtained structures with cellulases allow the selective removal of pure cellulose, whereas a TMSC pattern remains on the surface. These TMSC can be regenerated back to pure cellulose by treatments with vapors of hydrochloric acid. The developed methods allow the effective fabrication of micropatterned biopolymer thin films suitable for further functionalization and application in, e.g., bioanalytical devices. This is shown by the immobilization and detection of single-stranded DNA on structured cellulose surfaces. Owing to the versatility of both patterning approaches the methods can be further extended to other combinations of substrates and enzymes.

The conversion of trimethylsilyl cellulose (TMSC) to cellulose films via acid vapor hydrolysis is investigated at the gas solid interface in situ, in real time and under ambient conditions using the QCM-D technique. For this purpose, a permanent flow of gaseous HCl is employed which reacts with TMSC spun on QCM sensors to form cellulose films. The kinetics behind this reaction is elucidated and reveals first order. This desilylation reaction proceeds via a fast first phase ( k = 3.01 × 10 −3 s −1 ) and a second slower phase ( k = 6.29 × 10 −5 s −1 ) where less accessible silyl groups are cleaved off. Besides kinetics, film thicknesses have been determined using the QCM method. Moreover, the influence of the acid concentration on the kinetics and layer thickness was studied. A comparison between the materials synthesized in the QCM chamber with those obtained by classical vapor phase hydrolysis does not show any differences in the surface characteristics and composition as proven by X-ray photoelectron spectroscopy, atomic force microscopy, and wettability studies.

Summary: The adsorption behavior of laponite on cellulose model surfaces was studied by a quartz crystal microblance with dissipation (QCM-D). The influence of prior adsorption of a trihydroxysilane has also been investigated. XPS was used to determine the elemental composition of the surfaces.

tert-Butyl silanetriol behaves like a surfactant and self-assembles in aqueous and tetrahydrofuran (THF) solutions. Micelle formation was studied with pulsed field gradient stimulated spin echo (PFG-SSE) NMR, while multilayer lamellar vesicles can be concluded from small/wide angle X-ray scattering measurements in concentrated solutions at elevated temperature. The significant interaction between tert-butyl silanetriol and THF is further highlighted by a crystal structure featuring a 3:1 adduct of silanetriol and THF.

The anticoagulant activity of surfaces decorated with cellulose nanocrystals (CNCs) prepared via sulfuric acid hydrolysis, is explored. Such surfaces bear a high amount of negatively charged sulfate groups, which mimic the naturally occurring anticoagulant heparin in terms of charge density. It is demonstrated that CNC decorated surfaces significantly enhance the coagulation times of blood plasma and whole blood as proven by QCM-D and simple clotting tests.

Surface modifications of glass slides employing the sterically hindered tert-butyl substituted silanetriol are described. To the best of our knowledge, this is the first time that a stable silanetriol has been directly used for this purpose. So far unprecedented, this process runs under neutral aqueous conditions and in the absence of organic solvents, which makes coating protocols accessible to acid-sensitive substrates. The layer thickness and surface topography are investigated by the Sarfus technique, by X-ray reflectivity, and by atomic force microscopy (AFM). These techniques yield values of 0.8±0.1 (XRR) and 0.6±0.2 nm (Sarfus) for layer thickness and 0.33 nm for root mean square roughness (AFM). The modified surfaces have hydrophobic and oleophilic character and contact angles (CA) between 60° (formamide, CH2I2) and 90° (water) are obtained. The thin coatings allow a structuring by UV/ozone treatment in order to get hydrophilic and hydrophobic compartments on the surfaces. For all coatings, surface free energies are calculated using different models. To determine the isoelectric points (IEP) of the modified surfaces, we performed zeta-potential measurements. Correlations between zeta potentials and hydrophilicity of the surfaces are shown.

Twofold conjugate addition to a 2,6-dimesitylphenyl-substituted dihaloalkynylsilane yields a silyl-substituted 1-silaallene rather than the isomeric silyne. The dehalogenative intramolecular carbom...

For 2,6-dimesitylphenylsilanetriol (1), the nature of the solvent can control the structural motif in the solid state even without incorporation of the solvent into the structure. Silanetriol 1, for which an improved synthesis is reported, provides additional donor sites within the molecule which are able to compete with solvent molecules for coordination of the silanol functions. By using different crystallization conditions we have been able to realize three different supramolecular motifs, i.e. cluster, tube and discrete dimer, all stabilized by extended hydrogen bonding.

The formation of t-butyl substituted polyhedral silsesquioxanes (POSS) starting from the corresponding silanetriol is reported. Several intermediates involved in this complex condensation process could be identified spectroscopically. In addition, the initial condensation intermediate t-Bu(2)Si(2)O(OH)(4), as well as t-Bu(6)Si(6)O(9) and t-Bu(7)Si(7)O(9)(OH)(3), could be characterized by X-ray crystallography. Owing to the high crystal quality it was possible to experimentally determine the geometric parameters of the unusual cyclic hydrogen bond network in a dimeric POSS trisilanol for the first time. Furthermore, we investigated the structural changes concomitant with dimer formation/dissociation of the t-butyl substituted POSS trisilanol and its methyl analogue.

(Methylseleno)tri-n-butylphosphonium iodide has been prepared and was characterized by heteronuclear NMR spectra, ESI-MS and chemical analysis. The charge distribution and bond situation of its cation has been explored by quantum chemical methods at Hartree–Fock, DFT(B3LYP) and MP2 level. The results support a description as a selenenylphosphonium ion rather than as a donor stabilized selenenium ion. Treatment with methyl iodide yields Me3Se+I−, the crystal structure of which was reinvestigated.

The thermal condensation of phosphoryl triamide was reinvestigated and analyzed with ESI-MS as well as 31P- and 1H-NMR spectroscopy in the solid state and in solution. Our results indicate that strongly crosslinked polymers are formed even at temperatures lower than 300 °C; and, furthermore, evidence for facile partial hydrolysis of oligomeric condensation products on contact with water has been established using ESI-MS/MS.

This contribution summarizes achievements in the understanding of cellulose accessibility, structure, and function with a particular focus on its interactions with deuteration. This review is the first to explicitly devote a discussion to deuteration of cellulose and highlights remarkable new findings in cellulose research as a result of the development of new experimental approaches, from simple weighing of deuterated samples to sophisticated techniques such as small angle neutron scattering and 2H-NMR spectroscopy.

The supramolecular rearrangements of biopolymers have remained difficult to discern. Here, we present a versatile approach that allows for an in situ investigation of two major types of rearrangements typically observed with cellulose, the most abundant biopolymer on earth. Model thin films were employed to study time-resolved pore size changes using in situ grazing incidence small-angle X-ray scattering (GISAXS) during regeneration and drying.

The hydrolytic stability of the sterically protected dichlorosilane (Mes*O)2SiCl2 was investigated. The resulting products have been identified by electrospray mass spectrometry and, in the case of (Mes*O)2Si(OH)2, the crystal structure was obtained. Copyright © 2005 John Wiley & Sons, Ltd.

After an introduction to polysaccharides in general and cationic polysaccharides in particular, a short overview on different fields of applications in regenerative medicine is given. Applications are manifold and range from wound healing and artificial skins to guided nerve and bone regeneration. However, the scope of this chapter is to give a short overview on the topic by explaining important examples in detail.

The preparation, molecular structure, and metalation behavior of a sterically highly congested fluorosilane (tBuTipMeSiF) are described. This silane is subjected to dehydrofluorination under thermally mild conditions. A C-unsubstituted transient intermediate — either the silene or the corresponding silenoid — is generated in a metalation/elimination sequence at low temperatures, and this intermediate dimerizes to give the corresponding 1,3-disilacyclobutane exclusively, even in the presence of a trapping agent. The significant steric hindrance in the starting fluorosilane and the final 1,3-disilacyclobutane is corroborated by their crystal structures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

The first gas phase structure of a silanetriol, tert-butylsilane-triol [(t)BuSi(OH)(3)], determined by gas electron diffraction (GED), is reported. Quantum chemical calculations have been performed to elucidate potential intermolecular interactions between silanetriol molecules in the gas phase. The results are set into contrast to solid state structures of (t)BuSi(OH)(3) and related compounds.

In this study, the interaction of fluorescein isothiocyanate functionalized bovine serum albumin (FITC-BSA) with cellulose surfaces decorated with trimethyl chitosan (TMC) is investigated. Two types of TMC, one exhibiting a lower and one with a higher degree of cationization are used for protein adsorption. The adsorption is carried out at different pH values and concentrations of the protein solution. The amount, morphology and wettability of FITC-BSA coating on TMC/cellulose films are determined using quartz crystal microbalance with dissipation (QCM-D), atomic force microscopy, fluorescence microscopy and contact angle measurements. A lower pH and higher concentration of protein solution resulted in a greater amount of irreversibly adsorbed material owing to the reduced solubility and minimized electrostatic repulsion. A maximum adsorption of protein is observed on cellulose surfaces functionalized with TMC carrying a higher degree of cationization compared to TMC with a lower degree of cationization and pure cellulose surfaces at all applied concentrations and pH values. BSA is a commonly used model protein and is applied in this study to better understand its interaction with cationically rendered cellulose surfaces. Such knowledge is essential for creation of multifunctional polysaccharide-based biomaterials.

Herein, environmentally friendly surfactants based on new silanols as substitutes for the isoelectronic phosphonates were explored. Surface tensions of aqueous solutions are significantly reduced, particularly with those silanols that feature a high ratio of organic moiety to silanol. Besides their use as surfactants, their potential as coating agents for hydrophilic oxide surfaces was investigated for the example of glass substrates. In the solid-state sheet structures with silanol, double layers are present, in which the sheet spacing varies with the alkyl-chain length.

Unoxidized and carboxylated pullulan (obtained by pullulan oxidation using TEMPO-sodium hypochlorite-sodium bromide system) have been used as mediators for the silver nanoparticles formation (AgNPs), under environment-friendly conditions: using aqueous solutions, room temperature and notably, by using both mediators as reducing and stabilizing agents. The formation of AgNPs was first screened by measuring the surface plasmon resonance peak in the range of 380-440 nm using UV-vis spectroscopy. The morphology of the synthesized silver nanoparticles was determined by TEM, which indicated that the AgNPs differ on shape and thickness of the polymer shell by varying the silver nitrate concentration, different size and shape of AgNPs was achieved. The presence of elemental silver and the crystalline structure of the AgNPs were confirmed by EDX and XRD analyses. Moreover, the possible functional groups of pullulan (oxidized pullulan) responsible for the reduction and stabilization of AgNPs were evaluated using FT-IR. The results showed that both, pullulan and 6-carboxypullulan could be successfully used as reducing as well as capping agents for the AgNPs synthesis which shows potential antimicrobial activity against Gram positive and Gram negative bacteria.

A simple and highly reproducible synthesis of amorphous bismuth nanoparticles incorporated into a polysaccharide matrix using a photoreduction process is presented. As precursor for the generation of the Bi nanoparticles, organosoluble triphenylbismuth is used. The precursor is dissolved in toluene and mixed with a hydrophobic organosoluble polysaccharide, namely trimethylsilyl cellulose (TMSC) with high DSSi. The solution is subjected to UV exposure, which induces the homolytic cleavage of the bismuth-carbon bond in BiPh3 resulting in the formation of Bi(0) and phenyl radicals. The aggregation of the Bi atoms can be controlled in the TMSC matrix and yields nanoparticles of around 20 nm size as proven by TEM. The phenyl radicals undergo recombination to form small organic molecules like benzene and biphenyl, which can be removed from the nanocomposite after lyophilization and exposure to high vacuum. Finally, the TMSC matrix is converted to cellulose after exposure to HCl vapors, which remove the trimethylsilyl groups from the TMSC derivative. Although TMSC is converted to cellulose, the formed TMS-OH is not leaving the nanocomposite but reacts instead with surface oxide layer of the Bi nanoparticles to form silylated Bi nanoparticles as proven by TEM/EDX.

The use of cationic biopolymer surfaces for high protein binding affinity matrices is described. As model proteins, fluorescently labeled bovine serum albumins (FITC-BSA, TRITC-BSA) have been employed. The amount of proteins on such cationically rendered surfaces was quantified by QCM-D. In addition, flexible, transparent, patterned COP slides have been prepared and loaded with proteins ranging from 15 pM to 15 μM TRITC-BSA.

The crystal structure of the 2:1 adduct of trifluoroacetic acid and its sodium salt has been determined and its bond situation is compared to earlier descriptions based on IR spectroscopy and dissociation pressure measurements.

TEMPO enhances longitudinal relaxation rates of silicon compounds significantly (e.g., enhancement by a factor of 150 for Si(OEt)4) while tolerating a wide range of reactive functionalities making it a favorable alternative to other relaxation enhancers for 29Si NMR spectroscopy.

Owing to steric congestion, the phosphane unit within the title compound is dislocated from the central position which is associated with a difference in the PCC angles of 20.3(2)° and a compression of the Cl bond distance of the chlorine atom involved in this repulsive interaction. Copyright © 2006 John Wiley & Sons, Ltd.

Relativistic effects in triphenylbismuth have been investigated using a combined experimental and theoretical approach. The influence of these effects on the molecular structure (determined by gas electron diffraction) has been evaluated by means of quantum chemical calculations which consider scalar-relativistic and relativistic effects causing electronic spin-orbit coupling. Besides the molecular structure, different types of spectroscopic techniques (IR, NMR, UV-vis) have been applied and their results have been set in contrast with the results derived from quantum chemical calculations.

A high yield synthesis of the first silanedithiolate silanolate is reported which spontaneously assembles forming an inorganic rugby ball shaped 32 vertex polyhedral cluster stabilized by sterically demanding 2,6-dimesitylphenyl substituents and two LiCl units.

The preparation of water vapor barrier coatings composed of polyelectrolyte/clay multilayers using the layer-by-layer technique is reported. The suitability of different synthetic and renewable polyelectrolytes for the preparation of barrier coatings in combination with montmorillonite (MMT) platelets as well as the influence of the ionic strength and the number of bilayers on the coating performance was investigated. Highly hydrophilic and permeable cellulose films were used as substrate for determining the influence of the coatings on the water vapor transmission rate (WVTR). Improved barrier properties were realized by the use of polyethylene imine (PEI) or 2-hydroxy-3-trimethylammonium propyl chloride starch (HPMA starch) in combination with MMT. After the application of only 5 bilayers of PEI and MMT (thickness ∼40 nm) on each side of the cellulose film, the WVTR was significantly reduced. By the deposition of 40 PEI/MMT bilayers, the WVTR transmission rate was reduced by 68%. However, HPMA starch containing coatings led to vapor transmission reduction of up to 32% at the same number of coating steps. A strong correlation between the barrier properties of the coatings and the layer thickness was observed. The barrier properties of the coatings could be increased using higher ionic strengths. These results represent unprecedented water vapor barrier properties for coatings prepared from hydrophilic materials.

This chapter presents comprehensive information about surface phenomena of cellulose and polysaccharide surfaces. It comprises the necessary description of cellulose moieties, of measuring methods and recent results of polysaccharides surface modification and characterisation.

The object of the present study is the isodesmic reaction of cellobiose (the repeating unit in cellulose) with different kinds of silanes, R-SiH3, to form silylated cellobiose (Cello-SiH3) and the corresponding alcohols (R-OH). The size and the chemical reactivity of the substituent R is varied as well as the position where O-silylation at the cellobiose takes place. In contrast to experimental observations where the O6 position is favored for silylation, for the computed reactions, energy differences are smaller than 3 kcal/mol for the different positions at the B3LYP/6-311G* as well as at the B3LYP/6-311+G* level of theory. Depending on the silane, reaction energies in a range from -17 kcal/mol (R=NHSiH3) and +18 kcal/mol (R=F) have been calculated. In addition, semi-empirical calculations on the PM3 level of theory have been performed. These results are set into contrast with the results derived from DFT calculations to assess whether semi-empirical methods may be useful for the description of larger systems containing silylated cellobiose units.

The preparation of thin films of chitosan-silane hybrid materials by combining sol-gel processing and spin coating is reported. A variety of silanes can be used as starting materials for the preparation of such thin films, namely tetraethoxysilane, tri-tert-butoxysilanol, trimethylethoxysilane, p-trifluoromethyltetra-fluorophenyltriethoxysilane, trivinylmethoxysilane, (methoxymethyl)trimethyl-silane, and hexamethoxydisilane. These silanes are subjected to a sol-gel process before they are added to acidic chitosan solutions. The chitosan:silane ratio is kept constant at 6:1 (w/w) and dilutions with ethanol are prepared and spin coated. Depending on the degree of dilution, film thickness can be controlled in a range between 5 and 70 nm. For the determination of additional surface properties, static water contact angle measurements and atomic force microscopy have been employed.

The synthesis of a series of m-terphenyl-substituted tetrafluorosilicates with different cations (Na(+), K(+), Rb(+), Cs(+), Ag(+), Tl(+)) is described and the interactions between the anion and cation are investigated in the solid, solution, and gas states by using multinuclear NMR spectroscopy, X-ray diffraction, and ion cyclotron resonance Fourier-transform mass spectrometry (ICR-FT-MS). In solution, heteronuclear NMR spectroscopy parameters show only limited sensitivity to the nature of the cation, which furthermore can be affected by solvent effects. More pronounced effects are observed in the structural data obtained from X-ray diffraction studies, which are in good agreement with experimental gas-phase data from ESIMS. ESIMS also reveals the existence of dimeric species of the type [M(DmpSiF(4))(2)](-) (Dmp = 2,6-dimesitylphenyl), the stability of which was determined by normalized collision energy experiments.

The rational design of silver nanoparticles encapsulated in an anticoagulant, hemocompatible polysaccharide, 6-O-chitosan sulfate, is presented. Three different approaches are described for the immobilization of these core shell particles on cellulosic surfaces. The mass of the immobilized particles is quantified using a quartz crystal microbalance with dissipation (QCM-D). The antimicrobial activity of the surfaces towards E. coli MG 1655 [R1-16] is investigated by live/dead assays using fluorescence staining. All surfaces treated with the designed nanoparticles exhibit excellent antimicrobial activity towards E. coli MG 1655 [R1-16]. Anticoagulant properties of blood plasma on the nanoparticle treated surfaces have been determined using QCM-D. In comparison with the unmodified substrates, the total coagulation time as well as the thrombin formation time and fibrin clotting time of surfaces modified with nanoparticles are significantly increased.

The behavior of amorphous cellulose model thin films upon heat treatment is investigated. Upon heat treatment, a structural rearrangement in the films from a featureless to a fibrillar structure is observed which correlates with the regeneration time and total cellulose content as proven by atomic force microscopy and X-ray photoelectron spectroscopy. ATR-IR spectroscopy proves the presence of stronger hydrogen bonds in the heat treated surfaces which originate from a reorganization of the cellulose chains and pore structure. The rearrangement is accompanied with an increased surface hydrophobicity, a reduced swelling capacity and a reduction in the water content of the films. An increase in crystallinity of the films is not observed.