Plasma Surface Modification of Biomedical Polymers: Influence on Cell-Material Interaction

Polymers are commonly used in industry because of their excellent bulk properties, such as strength and good resistance to chemicals. Their surface properties are for most application inadequate due to their low surface energy. A surface modification is often needed, and plasma surface modification is used with success the past decades. In the past few years, also plasma surface modification for biomedical polymers has been investigated. For biomedical polymers, the surface properties need to be altered to promote a good cell adhesion, growth and proliferation and to make them suitable for implants and tissue engineering scaffolds. This review gives an overview of the use of plasma surface modification of biomedical polymers and the influence on cell-material interactions. First, an introduction on cell-material interaction and on antibacterial and antifouling surfaces will be given. Also, different plasma modifying techniques used for polymer surface modification will be discussed. Then, an overview of literature on plasma surface modification of biopolymers and the resulting influence on cell-material interaction will be given. After an overview of plasma treatment for improved cell-material interaction, plasma polymerization and plasma grafting techniques will be discussed. Some more specialized applications will be also presented: the treatment of 3D scaffolds for tissue engineering and the spatial control of cell adhesion. Antibacterial and antifouling properties, obtained by plasma techniques, will be discussed. An overview of research dealing with antibacterial surfaces created by plasma techniques will be given, antifouling surfaces will be discussed, and how blood compatibility can be improved by preventing protein adhesion.     

Does activation of the anti proton, rather than concertedness, determine the stereochemistry of base-catalyzed 1,2-elimination reactions? Anti stereospecificity in E1cB eliminations of β-3-trifluoromethylphenoxy esters, thioesters, and ketones

As part of a comprehensive investigation on the stereochemical aspects of base-catalyzed 1,2-elimination reactions, we have studied a set of acyclic carbonyl substrates that react by an irreversible E1cB mechanism with largely anti stereospecificity. (2)H NMR data show that these reactions using KOH in EtOH/H(2)O under non-ion-pairing conditions produce a minimum of 85-89% anti elimination on stereospecifically labeled tert-butyl (2R*,3R*)- and (2R*,3S*)-3-(3-trifluoromethylphenoxy)-2,3-(2)H(2)-butanoate, S-tert-butyl (2R*,3R*)- and (2R*,3S*)-3-(3-trifluoromethylphenoxy)-2,3-(2)H(2)-butanethioate, and the related ketones, (4R*,5R*)- and (4R*,5S*)-5-(3-trifluoromethylphenoxy)-4,5-(2)H(2)-3-hexanone. With both diastereomers of each substrate available, the KIEs can be calculated and the innate stereoselectivities determined. The elimination reactions of the β-3-trifluoromethylphenoxy substrates occur by E1cB mechanisms with diffusionally equilibrated enolate-anion intermediates. Thus, it is clear that anti elimination does not depend solely upon concerted E2 mechanisms. Negative hyperconjugation provides a satisfactory explanation for the anti stereospecificity exhibited by our carbonyl substrates, where the leaving group activates the anti proton, leading to the enolate intermediate. The activation of the anti proton by negative hyperconjugation may also play a role in the concerted pathways of E2 mechanisms. We have also measured the rates of the hydroxide-catalyzed elimination reactions of butanoate, thiobutanoate, and ketone substrates in EtOH/H(2)O, with β-tosyloxy, acetoxy, and 3-trifluoromethylphenoxy nucleofuges.     

Fast and selective sugar conversion to alkyl lactate and lactic acid with bifunctional carbon-silica catalysts

A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like carbon network. The particular structure of the carbon-silica composite allows the accommodation of a broad variety of catalytically active functions, useful to attain cascade reactions, in a readily tunable pore texture. The significance of a joint action of Lewis and weak Br?nsted acid sites was studied here to realize fast and selective sugar conversion. Lewis acidity is provided by grafting the silica component with Sn(IV), while weak Br?nsted acidity originates from oxygen-containing functional groups in the carbon part. The weak Br?nsted acid content was varied by changing the amount of carbon loading, the pyrolysis temperature, and the post-treatment procedure. As both catalytic functions can be tuned independently, their individual role and optimal balance can be searched for. It was thus demonstrated for the first time that the presence of weak Br?nsted acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the first step in the reaction network from triose to lactate. Composite catalysts with well-balanced Lewis/Br?nsted acidity are able to convert the trioses, glyceraldehyde and dihydroxyacetone, quantitatively into ethyl lactate in ethanol with an order of magnitude higher reaction rate when compared to the Sn grafted MCM-41 reference catalyst. Interestingly, the ability to tailor the pore architecture further allows the synthesis of a variety of amphiphilic alkyl lactates from trioses and long chain alcohols in moderate to high yields. Finally, direct lactate formation from hexoses, glucose and fructose, and disaccharides composed thereof, sucrose, was also attempted. For instance, conversion of sucrose with the bifunctional composite catalyst yields 45% methyl lactate in methanol at slightly elevated reaction temperature. The hybrid catalyst proved to be recyclable in various successive runs when used in alcohol solvent.     

Model-based analysis of dispersion curves using chirplets

Time-frequency representations, like the spectrogram or the scalogram, are widely used to characterize dispersive waves. The resulting energy distributions, however, suffer from the uncertainty principle, which complicates the allocation of energy to individual propagation modes (especially when the dispersion curves of these modes are close to each other in the time-frequency domain). This research applies the chirplet as a tool to analyze dispersive wave signals based on a dispersion model. The chirplet transform, a generalization of both the wavelet and the short-time Fourier transform, enables the extraction of components of a signal with a particular instantaneous frequency and group delay. An adaptive algorithm identifies frequency regions for which quantitative statements can be made about an individual mode's energy, and employs chirplets (locally adapted to a dispersion curve model) to extract the (proportional) energy distribution of that single mode from a multimode dispersive wave signal. The effectiveness of this algorithm is demonstrated on a multimode synthetic Lamb wave signal for which the ground-truth energy distribution is known for each mode. Finally, the robustness of this algorithm is demonstrated on real, experimentally measured Lamb wave signals by an adaption of a correlation technique developed in previous research.     

Reaction of 5-40 eV ions with self-assembled monolayers

The reaction of 5-40 eV O(+) and Ne(+) ions with alkanethiolate and semifluorinated alkanethiolate self-assembled monolayers (SAMs) is studied under ultrahigh vacuum (UHV) conditions. Whereas Ne(+) simply sputters fragments from the surface, O(+) can also abstract surface atoms and break C-C bonds in both the hydrocarbon and fluorocarbon SAM chains. Isotopic labeling experiments reveal that O(+) initially abstracts hydrogen atoms from the outermost two carbon atoms on an alkanethiolate SAM chain. However, the position of the isotopic label quickly becomes scrambled along the chain as the SAM is damaged through continuous ion bombardment. Scanning tunneling microscopy (STM) monitors changes in the SAM conformational structure at various stages during 5 eV ion bombardment. STM images indicate that O(+) reacts less efficiently with dodecanethiolate molecules packed internally within a structural domain than it does with molecules adsorbed at domain boundaries or near defect sites. STM images recorded after Ne(+) bombardment suggest that Ne(+) attacks the SAM exclusively near the domain boundaries. Taken collectively, these experiments advance our understanding of the degradation pathways suffered by polymeric satellite materials in the low-earth orbit (LEO) space environment.     

Sampling almonds for aflatoxin, part I: estimation of uncertainty associated with sampling, sample preparation, and analysis

Domestic and international regulatory limits have been established for aflatoxin in almonds and other tree nuts. It is difficult to obtain an accurate and precise estimate of the true aflatoxin concentration in a bulk lot because of the uncertainty associated with the sampling, sample preparation, and analytical steps of the aflatoxin test procedure. To evaluate the performance of aflatoxin sampling plans, the uncertainty associated with sampling lots of shelled almonds for aflatoxin was investigated. Twenty lots of shelled almonds were sampled for aflatoxin contamination. The total variance associated with measuring B1 and total aflatoxins in bulk almond lots was estimated and partitioned into sampling, sample preparation, and analytical variance components. All variances were found to increase with an increase in aflatoxin concentration (both B1 and total). By using regression analysis, mathematical expressions were developed to predict the relationship between each variance component (total, sampling, sample preparation, and analysis variances) and aflatoxin concentration. Variance estimates were the same for B1 and total aflatoxins. The mathematical relationships can be used to estimate each variance for a given sample size, subsample size, and number of analyses other than that measured in the study. When a lot with total aflatoxins at 15 ng/g was tested by using a 10 kg sample, a vertical cutter mixer type of mill, a 100 g subsample, and high-performance liquid chromatography analysis, the sampling, sample preparation, analytical, and total variances (coefficient of variation, CV) were 394.7 (CV, 132.4%), 14.7 (CV, 25.5%), 0.8 (CV, 6.1%), and 410.2 (CV, 135.0%), respectively. The percentages of the total variance associated with sampling, sample preparation, and analytical steps were 96.2, 3.6, and 0.2, respectively.     

Influence of statistical variations in cell distribution on the proliferation kinetics of Madin-Darby canine kidney cells on quartz crystal resonator

The influence of statistical variations in cell distribution on the proliferation of Madin-Darby canine kidney (MDCK-II) cells was analyzed. MDCK-II cells were cultivated in parallel on 4 quartz crystal resonators in a bioreactor chip. Results of proliferation experiments with different initial grade of confluence were compared. Light microscope pictures of the sensor surface and impedance spectra were continuously acquired. CFD simulation results of the bioreactor chip were employed to verify experimental conditions. Results show that especially at low confluency dissimilar development of non-confluent MDCK-II cell layers and resulting changes in acoustic load depend significantly on initial cell distribution.     

Slippage and nanorheology of thin liquid polymer films

Thin liquid films on surfaces are part of our everyday life; they serve, e.g.,?as coatings or lubricants. The stability of a thin layer is governed by interfacial forces, described by the effective interface potential, and has been subject of many studies in recent decades. In recent years, the dynamics of thin liquid films has come into focus since results on the reduction of the glass transition temperature raised new questions on the behavior of especially polymeric liquids in confined geometries. The new focus was fired by theoretical models that proposed significant implication of the boundary condition at the solid/liquid interface on the dynamics of dewetting and the form of a liquid front. Our study reflects these recent developments and adds new experimental data to corroborate the theoretical models. To probe the solid/liquid boundary condition experimentally, different methods are possible, each bearing advantages and disadvantages, which will be discussed. Studying liquid flow on a variety of different substrates entails a view on the direct implications of the substrate. The experimental focus of this study is the variation of the polymer chain length; the results demonstrate that inter-chain entanglements and in particular their density close to the interface, originating from non-bulk conformations, govern the liquid slip of a polymer.