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Escherichia coli (E. coli) is considered the most common life-threatening infectious bacteria in our daily life and poses a major challenge to human health. However, antibiotics frequently overused and misused has triggered increased multidrug resistance, hinders therapeutic outcomes, and causes higher mortalities. Herein, we addressed near-infrared (NIR) laser-excited human serum albumin (HSA) mediated graphene oxide loaded palladium nano-dots (HSA-GO-Pd) that can effectively combat Gram-negative E. coli in vitro. NIR laser-excited designed hybrid material highly generates singlet oxygen and hydroxyl radical by electron spin-resonance (ESR) analysis. Transmission electron microscope (TEM) images show small spherical sizes PdNPs on the surface of GO nano-sheets. The zeta (ζ) potential study indicates that in an aqueous medium, the average PdNPs size and surface capped charge comes from human body protein (HSA), HSA-GO-Pd is 5–8 nm, and +25 mV, respectively. The spectroscopic characterization reveals that in the synthesized HSA-GO-Pd nanocomposite, PdNPs successfully well-dispersed decorated on the surface of graphene oxide. The as-synthesized HSA-GO-Pd shows excellent antibacterial activity against gram-negative pathogen by killing 95% bacteria within 5 h. HSA-GO-Pd having very biocompatible and shows significant antibacterial activities. Owing to their intense photothermal conversation potential, low toxicity to normal cells, the as-addressed hybrid (HSA-GO-Pd) combined with NIR-irradiation will catch up valuable insight into the effective ablation of pathogenic bacteria.
Energy consumption by air-conditioning is expansive and leads to the emission of millions of tons of CO2 every year. A promising approach to circumvent this problem is the reflection of solar radiation: Rooms that would not heat up by irradiation will not need to be cooled down. Especially, transparent conductive metal oxides exhibit high infrared (IR) reflectivity and are commonly applied as low-emissivity coatings (low-e coatings). Indium tin oxide (ITO) coatings are the state-of-the-art application, though indium is a rare and expensive resource. This work demonstrates that aluminum-doped zinc oxide (AZO) can be a suitable alternative to ITO for IR-reflection applications. AZO synthesized here exhibits better emissivity to be used as roofing membrane coatings for buildings in comparison to commercially available ITO coatings. AZO particles forming the reflective coating are generated via solvothermal synthesis routes and obtain high conductivity and IR reflectivity without the need of any further post-thermal treatment. Different synthesis parameters were studied, and their effects on both conductive and optical properties of the AZO nanoparticles were evaluated. To this end, a series of characterization methods, especially 27Al-nuclear magnetic resonance spectroscopy (27Al-NMR) analysis, have been conducted for a deeper insight into the particles’ structure to understand the differences in conductivity and optical properties. The optimized AZO nanoparticles were coated on flexible transparent textile-based roofing membranes and tested as low-e coatings. The membranes demonstrated higher thermal reflectance compared with commercial ITO materials with an emissivity value lowered by 16%.
Controlled adhesion of HUVEC on polyelectrolyte multilayers by regulation of coating conditions
(2021)
Adhesion of host cells on the surface of implants is necessary for a healthy ingrowth of the implanted material. One possibility of surface modification is the coating of the implant with a second material with advantageous physical–chemical surface properties for the biological system. The coverage with blood proteins takes place immediately after implantation. It is followed by host–cell interaction on the surface. In this work, the effect of polyelectrolyte multilayer coatings (PEMs) on adhesion and activity of human umbilical vein endothelial cells (HUVECs) was studied. The PEMs were formed from poly(styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) from solutions with different concentrations of NaCl varying between 0 and 1.0 M. The adhesion of HUVEC and their viability on the PEM is related to the amount of adsorbed proteins from the applied cell growth medium. The amount of adsorbed proteins is controlled not only by the surface charge but also by the internal excess charge of the PEM. The internal excess charge of the PEM was controlled by changing the electrolyte concentration in the deposition solutions.
High moisture permeability, excellent mechanical properties in a wet state, high water-holding capability, and high exudate absorption make bacterial nanocellulose (BNC) a favorable candidate for biomedical device production, especially wound dressings. The lack of antibacterial activity and healing-promoting ability are the main drawbacks that limit its wide application. Pullulan (Pul) is a nontoxic polymer that can promote wound healing. Zinc oxide nanoparticles (ZnO-NPs) are well-known as a safe antibacterial agent. In this study, aminoalkylsilane was chemically grafted on a BNC membrane (A-g-BNC) and used as a bridge to combine BNC with Pul-ZnO-NPs hybrid electrospun nanofibers. FTIR results confirmed the successful production of A-g-BNC/Pul-ZnO. The obtained dressing demonstrated blood clotting performance better than that of BNC. The dressing showed an ability to release ZnO, and its antibacterial activity was up to 5 log values higher than that of BNC. The cytotoxicity of the dressing toward L929 fibroblast cells clearly showed safety due to the proliferation of fibroblast cells. The animal test in a rat model indicated faster healing and re-epithelialization, small blood vessel formation, and collagen synthesis in the wounds covered by A-g-BNC/Pul-ZnO. The new functional dressing, fabricated with a cost-effective and easy method, not only showed excellent antibacterial activity but could also accelerate wound healing.
Recently described rhizolutin and collinolactone isolated from Streptomyces Gç 40/10 share the same novel carbon scaffold. Analyses by NMR and X-Ray crystallography verify the structure of collinolactone and propose a revision of rhizolutins stereochemistry. Isotope-labeled precursor feeding shows that collinolactone is biosynthesized via type I polyketide synthase with Baeyer–Villiger oxidation. CRISPR-based genetic strategies led to the identification of the biosynthetic gene cluster and a high-production strain. Chemical semisyntheses yielded collinolactone analogues with inhibitory effects on L929 cell line. Fluorescence microscopy revealed that only particular analogues induce monopolar spindles impairing cell division in mitosis. Inspired by the Alzheimerprotective activity of rhizolutin, we investigated the neuroprotective effects of collinolactone and its analogues on glutamate-sensitive cells (HT22) and indeed, natural collinolactone displays distinct neuroprotection from intracellular oxidative stress.
Porous silica materials are often used for drug delivery. However, systems for simultaneous delivery of multiple drugs are scarce. Here we show that anisotropic and amphiphilic dumbbell core–shell silica microparticles with chemically selective environments can entrap and release two drugs simultaneously. The dumbbells consist of a large dense lobe and a smaller hollow hemisphere. Electron microscopy images show that the shells of both parts have mesoporous channels. In a simple etching process, the properly adjusted stirring speed and the application of ammonium fluoride as etching agent determine the shape and the surface anisotropy of the particles. The surface of the dense lobe and the small hemisphere differ in their zeta potentials consistent with differences in dye and drug entrapment. Confocal Raman microscopy and spectroscopy show that the two polyphenols curcumin (Cur) and quercetin (QT) accumulate in different compartments of the particles. The overall drug entrapment efficiency of Cur plus QT is high for the amphiphilic particles but differs widely between Cur and QT compared to controls of core–shell silica microspheres and uniformly charged dumbbell microparticles. Furthermore, Cur and QT loaded microparticles show different cancer cell inhibitory activities. The highest activity is detected for the dual drug loaded amphiphilic microparticles in comparison to the controls. In the long term, amphiphilic particles may open up new strategies for drug delivery.
Highly viscous bioinks offer great advantages for the three-dimensional fabrication of cell-laden constructs by microextrusion printing. However, no standardised method of mixing a high viscosity biomaterial ink and a cell suspension has been established so far, leading to non-reproducible printing results. A novel method for the homogeneous and reproducible mixing of the two components using a mixing unit connecting two syringes is developed and investigated. Several static mixing units, based on established mixing designs, were adapted and their functionality was determined by analysing specific features of the resulting bioink. As a model system, we selected a highly viscous ink consisting of fresh frozen human blood plasma, alginate, and methylcellulose, and a cell suspension containing immortalized human mesenchymal stem cells. This bioink is crosslinked after fabrication. A pre-crosslinked gellan gum-based bioink providing a different extrusion behaviour was introduced to validate the conclusions drawn from the model system. For characterisation, bioink from different zones within the mixing device was analysed by measurement of its viscosity, shape fidelity after printing and visual homogeneity. When taking all three parameters into account, a comprehensive and reliable comparison of the mixing quality was possible. In comparison to the established method of manual mixing inside a beaker using a spatula, a significantly higher proportion of viable cells was detected directly after mixing and plotting for both bioinks when the mixing unit was used. A screw-like mixing unit, termed “HighVisc”, was found to result in a homogenous bioink after a low number of mixing cycles while achieving high cell viability rates.
Human bestrophin-1 (hBest1) is a transmembrane Ca2+- dependent anion channel, associated with the transport of Cl−, HCO3- ions, γ-aminobutiric acid (GABA), glutamate (Glu), and regulation of retinal homeostasis. Its mutant forms cause retinal degenerative diseases, defined as Bestrophinopathies. Using both physicochemical - surface pressure/mean molecular area (π/A) isotherms, hysteresis, compressibility moduli of hBest1/sphingomyelin (SM) monolayers, Brewster angle microscopy (BAM) studies, and biological approaches - detergent membrane fractionation, Laurdan (6-dodecanoyl-N,N-dimethyl-2-naphthylamine) and immunofluorescence staining of stably transfected MDCK-hBest1 and MDCK II cells, we report:
1) Ca2+, Glu and GABA interact with binary hBest1/SM monolayers at 35 °C, resulting in changes in hBest1 surface conformation, structure, self-organization and surface dynamics. The process of mixing in hBest1/SM monolayers is spontaneous and the effect of protein on binary films was defined as “fluidizing”, hindering the phase-transition of monolayer from liquid-expanded to intermediate (LE-M) state;
2) in stably transfected MDCK-hBest1 cells, bestrophin-1 was distributed between detergent resistant (DRM) and detergent-soluble membranes (DSM) - up to 30 % and 70 %, respectively; in alive cells, hBest1 was visualized in both liquid-ordered (Lo) and liquid-disordered (Ld) fractions, quantifying protein association up to 35 % and 65 % with Lo and Ld. Our results indicate that the spontaneous miscibility of hBest1 and SM is a prerequisite to diverse protein interactions with membrane domains, different structural conformations and biological functions.
Unprecedented formation of sterically stabilized phospholipid liposomes of cuboidal morphology
(2021)
Sterically stabilized phospholipid liposomes of unprecedented cuboid morphology are formed upon introduction in the bilayer membrane of original polymers, based on polyglycidol bearing a lipid-mimetic residue. Strong hydrogen bonding in the polyglycidol sublayers creates attractive forces, which, facilitated by fluidization of the membrane, bring about the flattening of the bilayers and the formation of cuboid vesicles.
The article analyzes experimentally and theoretically the influence of microscope parameters on the pinhole-assisted Raman depth profiles in uniform and composite refractive media. The main objective is the reliable mapping of deep sample regions. The easiest to interpret results are found with low magnification, low aperture, and small pinholes. Here, the intensities and shapes of the Raman signals are independent of the location of the emitter relative to the sample surface. Theoretically, the results can be well described with a simple analytical equation containing the axial depth resolution of the microscope and the position of the emitter. The lower determinable object size is limited to 2–4 μm. If sub-micrometer resolution is desired, high magnification, mostly combined with high aperture, becomes necessary. The signal intensities and shapes depend now in refractive media on the position relative to the sample surface. This aspect is investigated on a number of uniform and stacked polymer layers, 2–160 μm thick, with the best available transparency. The experimental depth profiles are numerically fitted with excellent accuracy by inserting a Gaussian excitation beam of variable waist and fill fraction through the focusing lens area, and by treating the Raman emission with geometric optics as spontaneous isotropic process through the lens and the variable pinhole, respectively. The intersectional area of these two solid angles yields the leading factor in understanding confocal (pinhole-assisted) Raman depth profiles.
An advanced ‘clickECM’ that can be modified by the inverse-electron demand Diels-Alder reaction
(2021)
The extracellular matrix (ECM) represents the natural environment of cells in tissue and therefore is a promising biomaterial in a variety of applications. Depending on the purpose, it is necessary to equip the ECM with specific addressable functional groups for further modification with bioactive molecules, for controllable cross-linking and/or covalent binding to surfaces. Metabolic glycoengineering (MGE) enables the specific modification of the ECM with such functional groups without affecting the native structure of the ECM. In a previous approach (S. M. Ruff, S. Keller, D. E. Wieland, V. Wittmann, G. E. M. Tovar, M. Bach, P. J. Kluger, Acta Biomater. 2017, 52, 159–170), we demonstrated the modification of an ECM with azido groups, which can be addressed by bioorthogonal copper-catalyzed azide-alkyne cycloaddition (CuAAC). Here, we demonstrate the modification of an ECM with dienophiles (terminal alkenes, cyclopropene), which can be addressed by an inverse-electron-demand Diels-Alder (IEDDA) reaction. This reaction is cell friendly as there are no cytotoxic catalysts needed. We show the equipment of the ECM with a bioactive molecule (enzyme) and prove that the functional groups do not influence cellular behavior. Thus, this new material has great potential for use as a biomaterial, which can be individually modified in a wide range of applications.
Melamine-formaldehyde (MF) resins are widely used as surface finishes for engineered wood-based panels in decorative laminates. Since no additional glue is applied in lamination, the overall residual curing capacity of MF resins is of great technological importance. Residual curing capacity is measured by differential scanning calorimetry (DSC) as the exothermic curing enthalpy integral of the liquid resin. After resin synthesis is completed, the resulting pre-polymer has a defined chemical structure with a corresponding residual curing capacity. Predicting the residual curing capacity of a resin batch already at an early stage during synthesis would enable corrective measures to be taken by making adjustments while synthesis is still in progress. Thereby, discarding faulty batches could be avoided. Here, by using a batch modelling approach, it is demonstrated how quantitative predictions of MF residual curing capacity can be derived from inline Fourier Transform infrared (FTIR) spectra recorded during resin synthesis using partial least squares regression. Not only is there a strong correlation (R2 = 0.89) between the infrared spectra measured at the end of MF resin synthesis and the residual curing capacity. The inline reaction spectra obtained already at the point of complete dissolution of melamine upon methylolation during the initial stage of resin synthesis are also well suited for predicting final curing performance of the resin. Based on these IR spectra, a valid regression model (R2 = 0.85) can be established using information obtained at a very early stage of MF resin synthesis.
We report on the cure characterization, based on inline monitoring of the dielectric parameters, of a commercially available epoxy phenol resin molding compound with a high glass transition temperature (>195 °C), which is suitable for the direct packaging of electronic components. The resin was cured under isothermal temperatures close to general process conditions (165–185 °C). The material conversion was determined by measuring the ion viscosity. The change of the ion viscosity as a function of time and temperature was used to characterize the cross-linking behavior, following two separate approaches (model based and isoconversional). The determined kinetic parameters are in good agreement with those reported in the literature for EMCs and lead to accurate cure predictions under process-near conditions. Furthermore, the kinetic models based on dielectric analysis (DEA) were compared with standard offline differential scanning calorimetry (DSC) models, which were based on dynamic measurements. Many of the determined kinetic parameters had similar values for the different approaches. Major deviations were found for the parameters linked to the end of the reaction where vitrification phenomena occur under process-related conditions. The glass transition temperature of the inline molded parts was determined via thermomechanical analysis (TMA) to confirm the vitrification effect. The similarities and differences between the resulting kinetics models of the two different measurement techniques are presented and it is shown how dielectric analysis can be of high relevance for the characterization of the curing reaction under conditions close to series production.
Monodisperse polystyrene spheres are functional materials with interesting properties, such as high cohesion strength, strong adsorptivity, and surface reactivity. They have shown a high application value in biomedicine, information engineering, chromatographic fillers, supercapacitor electrode materials, and other fields. To fully understand and tailor particle synthesis, the methods for characterization of their complex 3D morphological features need to be further explored. Here we present a chemical imaging study based on three-dimensional confocal Raman microscopy (3D-CRM), scanning electron microscopy (SEM), focused ion beam (FIB), diffuse reflectance infrared Fourier transform (DRIFT), and nuclear magnetic resonance (NMR) spectroscopy for individual porous swollen polystyrene/poly (glycidyl methacrylate-co-ethylene di-methacrylate) particles. Polystyrene particles were synthesized with different co-existing chemical entities, which could be identified and assigned to distinct regions of the same particle. The porosity was studied by a combination of SEM and FIB. Images of milled particles indicated a comparable porosity on the surface and in the bulk. The combination of standard analytical techniques such as DRIFT and NMR spectroscopies yielded new insights into the inner structure and chemical composition of these particles. This knowledge supports the further development of particle synthesis and the design of new strategies to prepare particles with complex hierarchical architectures.
Melamine-formaldehyde resins are widely used for decorative paper impregnation. Resin properties relevant for impregnation are mainly determined already at the stage of resin synthesis by the applied reaction conditions. Thus, understanding the relationship between reaction conditions and technological properties is important. Response surface methodology based on orthogonal parameter level variations is the most suitable tool to identify and quantify factor effects and deduce causal correlation patterns. Here, two major process factors of MF resin synthesis were systematically varied using such a statistical experimental design. To arrive at resins having a broad range of technological properties, initial pH and M:F ratio were varied in a wide range (pH: 7.9–12.1; M:F ratio: 1:1.5–1:4.5). The impregnation behavior of the resins was modeled using viscosity, penetration rate and residual curing capacity as technological responses. Based on the response surface models, nonlinear and synergistic action of process factors was quantified and a suitable process window for preparing resins with favorable impregnation performance was defined. It was found that low M:F ratios (~1:2–1:2.5) and comparatively high starting pHs (~pH 11) yield impregnation resins with rapid impregnation behavior and good residual curing capacity.
We present the modification of ethylene-propylene rubber (EPM) with vinyltetra-methydisiloxane (VTMDS) via reactive extrusion to create a new silicone-based material with the potential for high-performance applications in the automotive, industrial and biomedical sectors. The radical-initiated modification is achieved with a peroxide catalyst starting the grafting reaction. The preparation process of the VTMDS-grafted EPM was systematically investigated using process analytical technology (in-line Raman spectroscopy) and the statistical design of experiments (DoE). By applying an orthogonal factorial array based on a face-centered central composite experimental design, the identification, quantification and mathematical modeling of the effects of the process factors on the grafting result were undertaken. Based on response surface models, process windows were defined that yield high grafting degrees and good grafting efficiency in terms of grafting agent utilization. To control the grafting process in terms of grafting degree and grafting efficiency, the chemical changes taking place during the modification procedure in the extruder were observed in real-time using a spectroscopic in-line Raman probe which was directly inserted into the extruder. Successful grafting of the EPM was validated in the final product by 1H-NMR and FTIR spectroscopy.
The effect of hard segment content and diisocyanate structure on the transparency and mechanical properties of soft poly(dimethylsiloxane) (PDMS)-based urea elastomers (PSUs) was investigated. A series of PSU elastomers were synthesized from an aminopropyl-terminated PDMS (M¯n: 16,300 g·mol−1), which was prepared by ring chain equilibration of the monomers octamethylcyclotetrasiloxane (D4) and 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS). The hard segments (HSs) comprised diisocyanates of different symmetry, i.e., 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI), 4,4′-methylenebis(phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI), and trans-1,4-cyclohexane diisocyanate (CHDI). The HS contents of the PSU elastomers based on H12MDI and IPDI were systematically varied between 5% and 20% by increasing the ratio of the diisocyanate and the chain extender APTMDS. PSU copolymers of very low urea HS contents (1.0–1.6%) were prepared without the chain extender. All PSU elastomers and copolymers exhibited good elastomeric properties and displayed elongation at break values between 600% and 1100%. The PSUs with HS contents below 10% were transparent and became increasingly translucent at HS contents of 15% and higher. The Young’s modulus (YM) and ultimate tensile strength values of the elastomers increased linearly with increasing HS content. The YM values differed significantly among the PSU copolymers depending on the symmetry of the diisocyanate. The softest elastomer was that based on the asymmetric IPDI. The elastomers synthesized from H12MDI and MDI both exhibited an intermediate YM, while the stiffest elastomer, i.e., that comprising the symmetric CHDI, had a YM three-times higher than that prepared with IPDI. The PSUs were subjected to load–unload cycles at 100% and 300% strain to study the influence of HS morphology on 10-cycle hysteresis behavior. At 100% strain, the first-cycle hysteresis values of the IPDI- and H12MDI-based elastomers first decreased to a minimum of approximately 9–10% at an HS content of 10% and increased again to 22–28% at an HS content of 20%. A similar, though less pronounced, trend was observed at 300% strain. First-cycle hysteresis among the PSU copolymers at 100% strain was lowest in the case of CHDI and highest in the IPDI-based elastomer. However, this effect was reversed at 300% strain, with CHDI displaying the highest hysteresis in the first cycle. In vitro cytotoxicity tests performed using HaCaT cells did not show any adverse effects, revealing their potential suitability for biomedical applications.
During curing of thermosetting resins the technologically relevant properties of binders and coatings develop. However, curing is difficult to monitor due to the multitude of chemical and physical processes taking place. Precise prediction of specific technological properties based on molecular properties is very difficult. In this study, the potential of principal component analysis (PCA) and principal component regression (PCR) in the analysis of Fourier transform infrared (FTIR) spectra is demonstrated using the example of melamine-formaldehyde (MF) resin curing in solid state. FTIR/PCA-based reaction trajectories are used to visualize the influence of temperature on isothermal cure. An FTIR/PCR model for predicting the hydrolysis resistance of cured MF resin from their spectral fingerprints is presented which illustrates the advantages of FTIR/PCR compared to the combination differential scanning calorimetry/isoconversional kinetic analysis. The presented methodology is transferable to the curing reactions of any thermosetting resin and can be applied to model other technologically relevant final properties as well.
Hypothesis
The origin of negative surface charge at water/air interface is still not clear. The most probable origin is specific adsorption of OH− ions. From diffuse layer potential, we can evaluate the surface density of ions in the Stern layer which can be a measure for the specific adsorption of ions and determines whether the surface charge is solely due to the specific adsorption of OH− ions.
Experiments
Equilibrium thickness of foam films of pure water and aqueous solutions of NaCl, HCl, and NaOH was measured as a function of disjoining pressure for water and as a function of concentration for the aqueous solutions at 298.15 K. Quartz-glass cells thoroughly cleaned and immersed in pure water before use were used for the measurement.
Findings
Application of a modified Poisson-Boltzmann equation to the equilibrium film thickness gave the diffuse layer potential and the surface density of ions in the Stern layer. From the concentration dependence of the surface density, it was concluded that not only OH− ions but also Cl− ions and HCO3− and/or CO32− ions adsorb specifically at the water/air interface.
Introduction: Bioresorbable collagenous barrier membranes are used to prevent premature soft tissue ingrowth and to allow bone regeneration. For volume stable indications, only non-absorbable synthetic materials are available. This study investigates a new bioresorbable hydrofluoric acid (HF)-treated magnesium (Mg) mesh in a native collagen membrane for volume stable situations. Materials and Methods: HF-treated and untreated Mg were compared in direct and indirect cytocompatibility assays. In vivo, 18 New Zealand White Rabbits received each four 8 mm calvarial defects and were divided into four groups: (a) HF-treated Mg mesh/collagen membrane, (b) untreated Mg mesh/collagen membrane (c) collagen membrane and (d) sham operation. After 6, 12 and 18 weeks, Mg degradation and bone regeneration was measured using radiological and histological methods. Results: In vitro, HF-treated Mg showed higher cytocompatibility. Histopathologically, HF-Mg prevented gas cavities and was degraded by mononuclear cells via phagocytosis up to 12 weeks. Untreated Mg showed partially significant more gas cavities and a fibrous tissue reaction. Bone regeneration was not significantly different between all groups. Discussion and Conclusions: HF-Mg meshes embedded in native collagen membranes represent a volume stable and biocompatible alternative to the non-absorbable synthetic materials. HF-Mg shows less corrosion and is degraded by phagocytosis. However, the application of membranes did not result in higher bone regeneration.
Controlling the surface properties and structure of thin nanosized coatings is of primary importance in diverse engineering and medical applications. Here we report on how the nanostructure, growth mechanism, thickness, roughness, and hydrophilicity of nanocomposites composed of weak natural or strong synthetic polyelectrolytes (PE) can be tailored by graphene oxide (GO) doping. GO reverses the build‐up mechanism affecting the internal structure and the hydrophilicity in a way depending on the type of the PE‐matrix. The extent of GO‐adsorption and its impact on the surface morphology was found to be independent on the type of the underlying PE‐matrix. The nanostructure of the hybrid films is not significantly altered when a single surface‐exposed GO‐layer is deposited, while increasing the number of embedded GO‐layers leads to pronounced surface heterogeneity. These results are expected to have valuable impact on the construction strategies of coatings with tunable surface properties.
Thermoplastic polymers like ethylene-octene copolymer (EOC) may be grafted with silanes via reactive extrusion to enable subsequent crosslinking for advanced biomaterials manufacture. However, this reactive extrusion process is difficult to control and it is still challenging to reproducibly arrive at well-defined products. Moreover, high grafting degrees require a considerable excess of grafting reagent. A large proportion of the silane passes through the process without reacting and needs to be removed at great expense by subsequent purification. This results in unnecessarily high consumption of chemicals and a rather resource-inefficient process. It is thus desired to be able to define desired grafting degrees with optimum grafting efficiency by means of suitable process control. In this study, the continuous grafting of vinyltrimethoxysilane (VTMS) on ethylene-octene copolymer (EOC) via reactive extrusion was investigated. Successful grafting was verified and quantified by 1H-NMR spectroscopy. The effects of five process parameters and their synergistic interactions on grafting degree and grafting efficiency were determined using a face-centered experimental design (FCD). Response surface methodology (RSM) was applied to derive a causal process model and define process windows yielding arbitrary grafting degrees between <2 and >5% at a minimum waste of grafting agent. It was found that the reactive extrusion process was strongly influenced by several second-order interaction effects making this process difficult to control. Grafting efficiencies between 75 and 80% can be realized as long as grafting degrees <2% are admitted.
Here, we report the continuous peroxide-initiated grafting of vinyltrimethoxysilane (VTMS) onto a standard polyolefin by means of reactive extrusion to produce a functionalized liquid ethylene propylene copolymer (EPM). The effects of the process parameters governing the grafting reaction and their synergistic interactions are identified, quantified and used in a mathematical model of the extrusion process. As process variables the VTMS and peroxide concentrations and the extruder temperature setting were systematically studied for their influence on the grafting and the relative grafting degree using a face-centered central composite design (FCD). The grafting degree was quantified by 1H NMR spectroscopy. Response surface methodology (RSM) was used to calculate the most efficient grafting process in terms of chemical usage and graft yield. With the defined processing window, it was possible to make precise predictions about the grafting degree with at the same time highest possible relative degree of grafting.
Azide-bearing cell-derived extracellular matrices (“clickECMs”) have emerged as a highly exciting new class of biomaterials. They conserve substantial characteristics of the natural extracellular matrix (ECM) and offer simultaneously small abiotic functional groups that enable bioorthogonal bioconjugation reactions. Despite their attractiveness, investigation of their biomolecular composition is very challenging due to the insoluble and highly complex nature of cell-derived matrices (CDMs). Yet, thorough qualitative and quantitative analysis of the overall material composition, organisation, localisation, and distribution of typical ECM-specific biomolecules is essential for consistent advancement of CDMs and the understanding of the prospective functions of the developed biomaterial. In this study, we evaluated frequently used methods for the analysis of complex CDMs. Sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) and (immune)histochemical staining methods in combination with several microscopic techniques were found to be highly eligible. Commercially available colorimetric protein assays turned out to deliver inaccurate information on CDMs. In contrast, we determined the nitrogen content of CDMs by elementary analysis and converted it into total protein content using conversion factors which were calculated from matching amino acid compositions. The amount of insoluble collagens was assessed based on the hydroxyproline content. The Sircol™ assay was identified as a suitable method to quantify soluble collagens while the Blyscan™ assay was found to be well-suited for the quantification of sulphated glycosaminoglycans (sGAGs). Eventually, we propose a series of suitable methods to reliably characterise the biomolecular composition of fibroblast-derived clickECM.
In recent years, the development and application of decellularized extracellular matrices (ECMs) for use as biomaterials have grown rapidly. These cell-derived matrices (CDMs) represent highly bioactive and biocompatible materials consisting of a complex assembly of biomolecules. Even though CDMs mimic the natural microenvironment of cells in vivo very closely, they still lack specifically addressable functional groups, which are often required to tailor a biomaterial functionality by bioconjugation. To overcome this limitation, metabolic glycoengineering has emerged as a powerful tool to equip CDMs with chemical groups such as azides. These small chemical handles are known for their ability to undergo bioorthogonal click reactions, which represent a desirable reaction type for bioconjugation. However, ECM insolubility makes its processing very challenging. In this contribution, we isolated both the unmodified ECM and azide-modified clickECM by osmotic lysis. In a first step, these matrices were concentrated to remove excessive water from the decellularization step. Next, the hydrogel-like ECM and clickECM films were mechanically fragmentized, resulting in easy to pipette suspensions with fragment sizes ranging from 7.62 to 31.29 μm (as indicated by the mean d90 and d10 values). The biomolecular composition was not impaired as proven by immunohistochemistry. The suspensions were used for the reproducible generation of surface coatings, which proved to be homogeneous in terms of ECM fragment sizes and coating thicknesses (the mean coating thickness was found to be 33.2 ± 7.3 μm). Furthermore, they were stable against fluid-mechanical abrasion in a laminar flow cell. When primary human fibroblasts were cultured on the coated substrates, an increased bioactivity was observed. By conjugating the azides within the clickECM coatings with alkyne-coupled biotin molecules, a bioconjugation platform was obtained, where the biotin–streptavidin interaction could be used. Its applicability was demonstrated by equipping the bioactive clickECM coatings with horseradish peroxidase as a model enzyme.
Most antimicrobial peptides (AMPs) and their synthetic mimics (SMAMPs) are thought to act by permeabilizing cell membranes. For antimicrobial therapy, selectivity for pathogens over mammalian cells is a key requirement. Understanding membrane selectivity is thus essential for designing AMPs and SMAMPs to complement classical antibiotics in the future. This study focuses on membrane permeabilization induced by SMAMPs and their selectivity for membranes with different lipid compositions. We measure release and fluorescence lifetime of a self-quenching dye in lipid vesicles. Apart from the dose-response, we quantify the strength of individual leakage events, and, employing cumulative kinetics, categorize permeabilization behavior. We propose that differing selectivities in a series of SMAMPs arise from a combination of the effect of the antimicrobial agent and the susceptibility of the membrane (with a given lipid composition) for certain types of leakage behavior. The unselective and hemolytic SMAMP is found to act mainly by the asymmetry stress mechanism, mediated by hydrophobic insertion of SMAMPs into lipid layers. The more selective SMAMPs induced leakage events occurring stochastically over several hours. Lipid intrinsic properties might additionally amplify the efficiency of leakage events. Leakage behavior changes with both the design of the SMAMP and the lipid composition of the membrane. Understanding how leakage behavior contributes to the selectivity and activity of antimicrobial agents will aid the design and screening of antimicrobials. An understanding of the underlying processes facilitates the comparison of membrane permeabilization across in vitro and in vivo assays.
Here, we study resin cure and network formation of solid melamine formaldehyde pre-polymer over a large temperature range viadynamic temperature curing profiles. Real-time infrared spectroscopy is used to analyze the chemical changes during network formation and network hardening. By applying chemometrics (multivariate curve resolution,MCR), the essential chemical functionalities that constitute the network at a given stage of curing are mathematically extracted and tracked over time. The three spectral components identified by MCR were methylol-rich, ether linkages-rich and methylene linkages-rich resin entities. Based on dynamic changes of their characteristic spectral patterns in dependence of temperature, curing is divided into five phases: (I) stationary phase with free methylols as main chemical feature, (II) formation of flexible network cross-linked by ether linkages, (III) formation of rigid, ether-cross-linked network, (IV) further hardening via transformation of methylols and ethers into methylene-cross-linkages, and (V) network consolidation via transformation of ether into methylene bridges. The presented spectroscopic/chemometric approach can be used as methodological basis for the functionality design of MF-based surface films at the stage of laminate pressing, i.e., for tailoring the technological property profile of cured MF films using a causal understanding of the underlying chemistry based on molecular markers and spectroscopic fingerprints.
The chemical synthesis of polysiloxanes from monomeric starting materials involves a series of hydrolysis, condensation and modification reactions with complex monomeric and oligomeric reaction mixtures. Real-time monitoring and precise process control of the synthesis process is of great importance to ensure reproducible intermediates and products and can readily be performed by optical spectroscopy. In chemical reactions involving rapid and simultaneous functional group transformations and complex reaction mixtures, however, the spectroscopic signals are often ambiguous due to overlapping bands, shifting peaks and changing baselines. The univariate analysis of individual absorbance signals is hence often only of limited use. In contrast, batch modelling based on the multivariate analysis of the time course of principal components (PCs) derived from the reaction spectra provides a more efficient tool for real time monitoring. In batch modelling, not only single absorbance bands are used but information over a broad range of wavelengths is extracted from the evolving spectral fingerprints and used for analysis. Thereby, process control can be based on numerous chemical and morphological changes taking place during synthesis. “Bad” (or abnormal) batches can quickly be distinguished from “normal” ones by comparing the respective reaction trajectories in real time. In this work, FTIR spectroscopy was combined with multivariate data analysis for the in-line process characterization and batch modelling of polysiloxane formation. The synthesis was conducted under different starting conditions using various reactant concentrations. The complex spectral information was evaluated using chemometrics (principal component analysis, PCA). Specific spectral features at different stages of the reaction were assigned to the corresponding reaction steps. Reaction trajectories were derived based on batch modelling using a wide range of wavelengths. Subsequently, complexity was reduced again to the most relevant absorbance signals in order to derive a concept for a low-cost process spectroscopic set-up which could be used for real-time process monitoring and reaction control.
Sol-Gel basierte Flammschutzmittel stellen einen vielversprechenden Ansatz für Textilien dar, gerade im Bereich des Ersatzes von derzeit etablierten halogenhaltigen Flammschutzmitteln. Letztere sind aufgrund ihrer toxikologisch Bedenklichkeit sowie ihrer mitunter bioakkumulierenden Eigenschaften in die Kritik geraten. In diesem Forschungsvorhaben wurde daher untersucht auf welche Weise ein Flammschutz per Sol-Gel-Ansatz auf Stickstoff- und/oder Phosphorbasis als halogenfreie Alternative verwirklicht werden kann. Die Sol-Gel-Schicht fungierte dabei zum einen als nicht brennbarer Binder, zum anderen konnten über das Einführen entsprechender funktioneller Seitenketten für den Flammschutz aktive Gruppen direkt mit eingebunden werden. Verschiedene Ansätze wurden dabei verfolgt. Vor allem durch die Nutzung von additivierten Systemen, d.h. durch Sol-Gel-Schichten mit Zusätzen von stickstoff- und/oder phosphorhaltigen Verbindungen konnte ein Flammschutz nach DIN EN ISO 15025 (Schutzkleidung – Schutz gegen Hitze und Flammen) erhalten werden. Anhand eines Modellsystems, bei dem in zwei aufeinanderfolgenden Schritten zuerst eine funktionalisierte Sol-Gel-Schicht und anschließend eine Phosphorverbindung in einem zweiten Schritt aufgebracht wurde, konnten die Vorteile des Flammschutzes auf Sol-Gel-Basis nachgewiesen werden. Dabei wurde unter anderem auch gezeigt, dass ein Mechanismus auf Basis der Bildung einer Schutzschicht hauptsächlich verantwortlich für den Flammschutz ist. Dieses Ergebnis ist für eine zukünftige, weitere Optimierung entsprechender Ausrüstungen nicht zu unterschätzen. Durch Ausrüstungsversuche im semi-industriellen Maßstab konnte weiterhin gezeigt werden, dass einer großtechnischen Umsetzung der angewandten Ausrüstungen prinzipiell nichts im Wege steht. Abstriche müssen bis dato lediglich bezüglich der Waschstabilität gemacht werden. Die Sol-Gel-Schichten überstanden zwar im allgemeinen typische Waschprozesse, eine Permanenz der Flammfestigkeit von additivierten Systemen ergab sich aber nur in einzelnen Fällen. Ausgehend von den Ergebnissen wurde ein neuer Ansatz vorgestellt, der über den hier zugrundeliegenden Ansatz hinausgeht. Dieser sieht vor, durch den Einsatz von neu-synthetisierten Silanen mit Stickstoff- und Phosphorgruppen Sol-Gel-Schichten herzustellen, die ein vielversprechendes Verhalten zeigen. Hier konnte auch nach ersten Waschtests eine Aufrechterhaltung der verbesserten Flammfestigkeit nachgewiesen werden. Insgesamt konnte innerhalb des Forschungsvorhabens gezeigt werden, dass ein Flammschutz auf Sol-Gel-Basis für Textilien erhalten werden kann. Darüberhinaus konnte auch erklärt werden auf welchem Mechanismus dieser Flammschutz begründet ist und wie die derzeit noch ungenügende Waschpermanenz verbessert werden kann.
We investigate the toxicity of different types and sizes of microplastic particles (0.3–4 mm) under different conditions (new particles, aged particles with biofilm, and particles with adsorbed Tributyltin) on the freshwater amphipod Gammarus fossarum in 3-week exposures. All types of plastic particles, which were randomly taken up to a small extent, were mostly Polyphenylenoxide, Polybutylentherephthalate and Polypropylene, with particles < 1 mm in size. Plastic particles did not affect the feeding and locomotory behaviour of gammarids, and there was no strong difference between pristine plastic particles and aged particles with biofilm. Mortality tended to be higher compared with the control. Tributyltinhydride (TBTH) adsorbed to microplastic particles had no effect on uptake, survival, feeding and locomotory behaviour during the 3 weeks of exposure. Dissolved TBTH, however, was already very toxic after few days of exposure (LC50-96h < 1 ng l–1).
Kostenkalkulation im Anlagenbau: Modell zur Bewertung der Konkurrenzfähigkeit im Entwicklungsstadium
(2020)
Während Grundchemikalien größtenteils im industriellen Maßstab mittels verfahrenstechnisch optimierter Großanlagen hergestellt werden, entwickeln Forschungsinstitute biobasierte Prozesse zur Herstellung von Plattformchemikalien im Labor- und Pilotmaßstab. Im Rahmen dieser Arbeit wird ein Kostenkalkulationsmodell zur Abschätzung der Investitions- und Betriebskosten verfahrenstechnischer Anlagen vorgestellt, auf dessen Basis die ökonomische Konkurrenzfähigkeit in der Entwicklung befindlicher Verfahren ermittelt werden kann. Das Modell ist fur Anwendungen im industriellen Maßstab
geeignet.
Hyperspectral imaging opens a wide field of applications. It is a well established technique in agriculture, medicine, mineralogy and many other fields. Most commercial hyperspectral sensors are able to record spectral information along one spatial dimension in a single acquisition. For the second spatial dimension a scan is required. Beside those systems there is a novel technique allowing to sense a two dimensional scene and its spectral information within one shot. This increases the speed of hyperspectral imaging, which is interesting for metrology tasks under rough environmental conditions. In this article we present a detailed characterization of such a snapshot sensor for later use in a snapshot full field chromatic confocal system. The sensor (Ximea MQ022HG-IM-SM5X5-NIR) is based on the so called snapshot mosaic technique, which offers 25 bands mapped to one so called macro pixel. The different bands are realized by a spatially repeating pattern of Fabry-Pèrot flters. Those filters are monolithically fabricated on the camera chip.
The critical process parameters cell density and viability during mammalian cell cultivation are assessed by UV/VIS spectroscopy in combination with multivariate data analytical methods. This direct optical detection technique uses a commercial optical probe to acquire spectra in a label-free way without signal enhancement. For the cultivation, an inverse cultivation protocol is applied, which simulates the exponential growth phase by exponentially replacing cells and metabolites of a growing Chinese hamster ovary cell batch with fresh medium. For the simulation of the death phase, a batch of growing cells is progressively replaced by a batch with completely starved cells. Thus, the most important parts of an industrial batch cultivation are easily imitated. The cell viability was determined by the well-established method partial least squares regression (PLS). To further improve process knowledge, the viability has been determined from the spectra based on a multivariate curve resolution (MCR) model. With this approach, the progress of the cultivations can be continuously monitored solely based on an UV/VIS sensor. Thus, the monitoring of critical process parameters is possible inline within a mammalian cell cultivation process, especially the viable cell density. In addition, the beginning of cell death can be detected by this method which allows us to determine the cell viability with acceptable error. The combination of inline UV/VIS spectroscopy with multivariate curve resolution generates additional process knowledge complementary to PLS and is considered a suitable process analytical tool for monitoring industrial cultivation processes.
Hypericin is one of the most efficient photosensitizers used in photodynamic tumor therapy (PDT). The reported treatments of this drug reach from antidepressive, antineoplastic, antitumor and antiviral activity. We show that hypericin can be optically detected down to a single molecule at ambient conditions. Hypericin can even be observed inside of a cancer cell, which implies that this drug can be directly used for advanced microscopy techniques (PALM, spt-PALM, or FLIM). Its photostability is large enough to obtain single molecule fluorescence, surface enhanced Raman spectra (SERS), fluorescence lifetime, antibunching, and blinking dynamics. Sudden spectral changes can be associated with a reorientation of the molecule on the particle surface. These properties of hypericin are very sensitive to the local environment. Comparison of DFT calculations with SERS spectra show that both the neutral and deprotonated form of hypericin can be observed on the single molecule and ensemble level.
Although integrins are responsible for the interaction of cells with their environment, e.g., the extracellular matrix or artificial substrates, there is still a lack of knowledge about their role in cell adhesion and migration on protein-coated substrates with microtopography. Understanding such interactions could lead to new applications in e.g., medical implants as well as shed light on processes such as embryonic development, angiogenesis, wound healing, and tumor progression. In this work, the influence of surface topography and chemistry on αvβ3 and α5β1 integrin-mediated cell adhesion and migration of healthy and malignant human cell types (human coronary artery endothelial cells, human osteosarcoma cells, and human skin fibroblasts cells) was studied, using microgrooved and flat substrates covered by two different extracellular proteins, fibronectin and vitronectin. Although some general behaviors can be observed, cell migration (speed, directionality, and persistence time) and morphological adaptation (cell area, aspect ratio, and circularity) of cells on protein coated microgrooved substrates are mainly dependent on the cell type and its specific integrin expression.
Cancer cells invade confined microchannels via a self-directed mesenchymal-to-amoeboid transition
(2019)
Cancer cell invasion through physical barriers in the extracellular matrix (ECM) requires a complex synergy of traction force against the ECM, mechanosensitive feedback, and subsequent cytoskeletal rearrangement. PDMS microchannels were used to investigate the transition from mesenchymal to amoeboid invasion in cancer cells. Migration was faster in narrow 3 μm-wide channels than in wider 10 μm channels, even in the absence of cell-binding ECM proteins. Cells permeating narrow channels exhibited blebbing and had smooth leading edge profiles, suggesting an ECM-induced transition from mesenchymal invasion to amoeboid invasion. Live cell labeling revealed a mechanosensing period in which the cell attempts mesenchymal-based migration, reorganizes its cytoskeleton, and proceeds using an amoeboid phenotype. Rho/ROCK (amoeboid) and Rac (mesenchymal) pathway inhibition revealed that amoeboid invasion through confined environments relies on both pathways in a time- and ECM dependent manner. This demonstrates that cancer cells can dynamically modify their invasion programming to navigate physically confining matrix conditions.
Melamine–formaldehyde (MF) resins are widely used as adhesives and finishing materials in the wood industry. During resin cure, either methylene ether or methylene bridges are formed, leading to the formation of a three‐dimensional resin network. Not only the curing degree, but also the chemical species present in the cured resin determine the quality of the final product. Analytical methods allowing a detailed investigation of network formation are of great benefit to manufacturers. In the present work, resin cure of an MF precondensate is studied at different temperatures (100–200 °C) without considering the initial pH as a factor. Isoconversional kinetic analysis based on exothermal curing enthalpies enables calculation of the crosslinking degree at a given time/temperature regime. A semiquantitative determination of the chemical groups present is performed based on solid‐state nuclear magnetic resonance data. Fourier transform infrared spectroscopy has shown to be a fast and reliable analytical tool with high sensitivity toward functional groups and with great potential for at‐line process control.
Hauptziel des Projektes war zum einen die Entwicklung einer validen Testmethode auf Grundlage vorliegender Normen, welche die in der betrieblichen Praxis auftretende Degradation abreinigbarer Filtermedien (hohe Temperaturen, aggressive chemische Atmosphären) praxisnah abbilden kann. Die Methode sollte auch die mechanische Alterung der Medien durch Staubbeaufschlagung sowie Abreinigungs Druckstöße berücksichtigen (DIN ISO 11057). Innerhalb des Projektes konnten umfangreiche Praxiserfahrungen mit der Inbetriebnahme und dem Betrieb einer schadgasbeaufschlagten, temperierbaren Testkammer zur chemischen Alterung von Filtermedien auf Grundlage der Vorgaben der DIN EN ISO 16891 gewonnen werden. Sollen vergleichbare Prüfdaten für mehrere Proben verlässlich ermittelt werden, sind bei den Untersuchungen demnach umfangreiche Randbedingungen zu beachten. Insbesondere zeigten die Untersuchungen den hohen technischen Aufwand zur Durchführung der Filtertests auf, welche nicht zuletzt auch aufgrund der erforderlichen Sicherheitstechnik und langen Untersuchungsdauer eine Umsetzung insbesondere bei KMU aus wirtschaftlichen Gründen erschwert ist. Es konnte weiter dargestellt werden, dass die Kombination von chemisch-thermischer und mechanisch(-thermischer) Alterung durch den Einsatz verschiedener Prüfeinrichtungen grundsätzlich umsetzbar ist. Die im Rahmen des Vorhabens entwickelte Testmethode einer chemischen Alterung der Filtermatrices durch Gasphasenexposition in einer Druckkammer ermöglicht kürzere Beanspruchungszeiträume bei reduziertem zu behandelnden Schadgasanfall und kann damit den wirtschaftlichen Betrieb eines entsprechenden Prüfstandes ermöglichen. Kombiniert mit der externen mechanischen Alterung durch Staubbeaufschlagung und Möglichkeit der parallelen Temperaturaufprägung gem. EN ISO 16891 auf mehrere Filtermedien-Proben lässt sich das thermisch, chemisch und mechanisch induzierte Degradationsverhalten von Filtermedien ggf. realitätsnah und mit wirtschaftlich vertretbarem Aufwand in eine Prüfvorschrift überführen. Entsprechende Validierungsarbeiten sind Bestandteil eines aktuell gestarteten Folgeprojektes. Das zweite Hauptziel des Projektes war es Ausrüstungen zu entwickeln, die zu einer verbesserten Beständigkeit gegenüber aggressiven Komponenten führen. Die Ergebnisse zeigten, dass mit dem Sol-Gelverfahren mechanisch stabile Beschichtungen auf Faservlies dauerhaft aufgetragen werden konnten, welche insbesondere die chemisch induzierte Degradation von Aramiden reduzieren können. Bei Aramiden handelt es sich um relativ teure Hochleistungsmaterialien, von welchen bekannt ist, dass ihre Beständigkeit sowohl gegen über UV-Strahlung als auch unterschiedlichen Schadgasen gering ist. Daher stellen die Beständigkeit der Materialien verbessernde Ausrüstungen eine wichtige Entwicklung für Unternehmen dar, um auf diese Weise beständigere Aramid-basierte Produkte zu erhalten. Als besonders geeignet stellten sich dabei Fluorcarbonausrüstungen, organisch-anorganische Hybride auf Basis von GPTMS und Zirkonium-haltige Ausrüstungen heraus.
The current paper studies the influence of geometrical parameters of the fused deposition modeling (FDM) - fused filament fabrication (FFF) 3D printing process on printed part strength for open source desktop 3D printers and the most popular material used for that purpose - i.e., polylactic acid (PLA). The study was conducted using a set of different nozzles (0.4, 0.6, and 0.8 mm) and a range of layer heights from the minimum to maximum physical limits of the machine. To assess print strength, a novel assessment method is proposed. A tubular sample is loaded in the weakest direction (across layers) in a three point bending fixture. Mesostructure evaluation through scanning electronic microscopy (SEM) scans of the samples was used to explain the obtained results. We detected a significant influence of geometric process parameters on sample mesostructure, and consequently, on sample strength.
So far, only few authors addressed the serum-free, defined differentiation of adipocytes. And there are hardly any trials available on the defined maintenance of adipocytes. In this study, the development of a defined culture medium for the adipogenic differentiation of primary human adipose-derived stem cells (ASCs) was aimed. Based on the addition of specific factors for the replacement of serum, ASCs were differentiated to viable and characteristic adipocytes for 14 days, which was proven through the accumulation of lipids, the expression of perilipin A and by the release of leptin and glycerol. Furthermore, a defined maintenance medium was developed, which supported the maturation and stability of cells for a long-term period of additional 42 days until day 56.
Palladium-doped silica materials with SiCH3 groups were fabricated by sol-gel method under various calcination atmospheres and membranes were made thereof by coating process. The results showed that air atmosphere can lead to the partial oxidation of metallic Pd0 to PdO while N2 and H2 atmospheres can effectively prevent metallic Pd0 from being oxidized. H2 atmosphere is proved to be a more prominent way to slow down the decomposition of organic SiCH3 group than N2 and air atmospheres. The surface area, micropore volume and porosity of palladium-doped silica membrane material calcined in H2 atmosphere are much higher than those calcined in N2 atmosphere. Compared with N2 atmosphere, the palladium-doped silica membranes calcined in H2 atmosphere showed higher H2 permeability and H2/CO2 selectivity before and after the steam exposure. The apparent activation energy of H2 permeation through the palladium-doped silica membrane calcined under H2 atmosphere (2.51 ± 0.05 kJ/mol) was slightly lower than that calcined under N2 atmosphere (2.84 ± 0.04 kJ/mol). Calcination atmosphere plays some role in membrane performance, which has greater influence on the permeance than on the gas permselectivity. Calcination under H2 atmosphere is well conducive to improve the gas permeance and H2 permselectivity of palladium-doped silica membrane.
Der ultraschnelle Mechanismus der Alken-Hydrosylilierung lässt sich von den Flüssigsiliconen (LSRs) auf VNB-EPDM-Mischungen übertragen. In der Verarbeitung würde diese für VNB-EPDM die Wettbewerbsfähigkeit hinsichtlich realisierbarer kürzester Zykluszeiten und neue Marktsegmente alternativ zu den LSR-Materialien eröffnen, u.a. in speziellen Dichtungsanwendungen. Peroxidisch vernetzte EPDM-Mischungen können in wässrig-sauren und wässrig-alkalischen Medien eine bessere chemische Beständigkeit als LSR-Materialien bieten. Sie sind duch die radikalische Vernetzung in der Kinetik aber im Vergleich zu additionsvernetzbaren Elastomeren als deutlich träger einzustufen. Ein weiterer Aspekt ist die Permeationsbeständigkeit gegenüber Gasen und Lösemitteldämpfen, die in dieser Arbeit näher untersucht worden ist. In dieser Eigenschaft unterscheiden sich VNB-EPDM und LSR deutlich voneinander. Mit der Bestimmung von zeit- und temperaturabhängigen Permeationsraten von n-Hexan-Lösemitteldämpfen erfolgt ein Vergleich beider Elastomerklassen. Auf die Theorie der Gaspermeation und der sogenannten Pervaporation wird grundlegend eingegangen und zusätzlich der weitere Einfluss von Rezepturbestandteilen beleuchtet. Des Weiteren werden stationäre Permeationskoeffizienten für die Lösemittel-Dampf-Evaporation berechnet, indem die Ausprägung des Quelldrucks im Inneren der Elastomerwerkstoffe durch signifikante Volumenquellungen als eigentliche Triebkraft herangeszogen wird.
An ultraviolet visible (UV–Vis) spectroscopy method was developed that can quantitatively characterize a technical copper surface to determine oxide layers and organic impurities. The oxide layers were produced by a heating step at 175 ℃ for four different times (range = 1–10 min). Partial least squares (PLS) regression was used to establish a relation between the UV–Vis spectra and film thickness measurements using Auger electron spectroscopy depth profiles. The validation accuracy of the regression is in the range of approximately 2.3 nm. The prediction model allowed obtaining an estimation of the oxide layer thickness with an absolute error of 2.9 nm. Alternatively, already known methods cannot be used because of the high roughness of the technical copper surfaces. An integrating sphere is used to measure the diffuse reflectance of these surfaces, providing an average over all angles of illumination and observation.
A wide variety of cell types exhibit substrate topography-based behavior, also known as contact guidance. However, the precise cellular mechanisms underlying this process are still unknown. In this study, we investigated contact guidance by studying the reaction of human endothelial cells (ECs) to well-defined microgroove topographies, both during and after initial cell spreading. As the cytoskeleton plays a major role in cellular adaptation to topographical features, two methods were used to perturb cytoskeletal structures. Inhibition of actomyosin contractility with the chemical inhibitor blebbistatatin demonstrated that initial contact guidance events are independent of traction force generation. However, cell alignment to the grooved substrate was altered at later time points, suggesting an initial ‘passive’ phase of contact guidance, followed by a contractility-dependent ‘active’ phase that relies on mechanosensitive feedback. The actin cytoskeleton was also perturbed in an indirect manner by culturing cells upside down, resulting in decreased levels of contact guidance and suggesting that a possible loss of contact between the actin cytoskeleton and the substrate could lead to cytoskeleton impairment. The process of contact guidance at the microscale was found to be primarily lamellipodia driven, as no bias in filopodia extension was observed on micron-scale grooves.
Structural and functional thermosetting composite materials are exposed to different kinds of stress which can damage the polymer matrix, thus impairing the intended properties. Therefore, self-healing materials have attracted the attention of many research groups over the last decades in order to provide satisfactory material properties and outstanding product durability. The present article provides a critical overview of promising self-healing strategies for crosslinked thermoset polymers. It is organized in two parts: an overview about the different approaches to self-healing is given in the first part, whereas the second part focuses on the specific chemistries of the main strategies to achieve self-healing through crosslinking. It is attempted to provide a comprehensive discussion of different approaches which are described in the scientific literature. By comparison of the advantages and disadvantages, the authors wish to provide helpful insights on the assessment of the potential to transfer the extensive present knowledge about self-healing materials and methods to surface varnishing thermoset coatings.
This paper presents an approach for label-free brain tumor tissue typing. For this application, our dual modality microspectroscopy system combines inelastic Raman scattering spectroscopy and Mie elastic light scattering spectroscopy. The system enables marker-free biomedical diagnostics and records both the chemical and morphologic changes of tissues on a cellular and subcellular level. The system setup is described and the suitability for measuring morphologic features is investigated.
Energy transfer kinetics in photosynthesis as an inspiration for improving organic solar cells
(2017)
Clues to designing highly efficient organic solar cells may lie in understanding the architecture of light harvesting systems and exciton energy transfer (EET) processes in very efficient photosynthetic organisms. Here, we compare the kinetics of excitation energy tunnelling from the intact phycobilisome (PBS) light harvesting antenna system to the reaction center in photosystem II in intact cells of the cyanobacterium Acaryochloris marina with the charge transfer after conversion of photons into photocurrent in vertically aligned carbon nanotube (va- CNT) organic solar cells with poly(3-hexyl)thiophene (P3HT) as the pigment. We find that the kinetics in electron hole creation following excitation at 600 nm in both PBS and va-CNT solar cells to be 450 and 500 fs, respectively. The EET process has a 3 and 14 ps pathway in the PBS, while in va-CNT solar cell devices, the charge trapping in the CNT takes 11 and 258 ps. We show that the main hindrance to efficiency of va CNT organic solar cells is the slow migration of the charges after exciton formation.
In vitro cultured cells produce a complex extracellular matrix (ECM) that remains intact after decellularization. The biological complexity derived from the variety of distinct ECM molecules makes these matrices ideal candidates for biomaterials. Biomaterials with the ability to guide cell function are a topic of high interest in biomaterial development. However, these matrices lack specific addressable functional groups, which are often required for their use as a biomaterial. Due to the biological complexity of the cell-derived ECM, it is a challenge to incorporate such functional groups without affecting the integrity of the biomolecules within the ECM. The azide-alkyne cycloaddition (click reaction, Huisgen-reaction) is an efficient and specific ligation reaction that is known to be biocompatible when strained alkynes are used to avoid the use of copper (I) as a catalyst. In our work, the ubiquitous modification of a fibroblast cell-derived ECM with azides was achieved through metabolic oligosaccharide engineering by adding the azide-modified monosaccharide Ac4GalNAz (1,3,4,6 tetra-O-acetyl-N-azidoacetylgalactosamine) to the cell culture medium. The resulting azide-modified network remained intact after removing the cells by lysis and the molecular structure of the ECM proteins was unimpaired after a gentle homogenization process. The biological composition was characterized in order to show that the functionalization does not impair the complexity and integrity of the ECM. The azides within this ‘‘clickECM” could be accessed by small molecules (such as an alkyne modified fluorophore) or by surface-bound cyclooctynes to achieve a covalent coating with clickECM.
Indium tin oxide (ITO) particle coatings are known for high transparency in the visible, good conductive properties and near-infrared absorption. These properties depend on ITO particle's stiochiometric composition, defects and size. Here we present a method to gradually change ITO particle's optical properties by a simple and controlled laser irradiation process. The defined irradiation process and controlled energy dose input allows one to engineer the absorption and transsmission of coatings made from these particles. We investigate the role of the surrounding solvent, influence of laser fluence and the specific energy dose targeting modification of the ITO particle's morphology and chemistry by stepwise laser irradiation in a free liquid jet. TEM, SEM, EDX, XPS, XRD and Raman are used to elucidate the structural, morphological and chemical changes of the laser-induced ITO particles. On the basis of these results the observed modification of the optical properties is tentatively attributed to chemical changes, e.g. laser-induced defects or partial reduction.
We report the temperature dependence of metal-enhanced fluorescence (MEF) of individual photosystem I (PSI) complexes from Thermosynechococcus elongatus (T. elongatus) coupled to gold nanoparticles (AuNPs). A strong temperature dependence of shape and intensity of the emission spectra is observed when PSI is coupled to AuNPs. For each temperature, the enhancement factor (EF) is calculated by comparing the intensity of individual AuNP-coupled PSI to the mean intensity of ‘uncoupled’ PSI. At cryogenic temperature (1.6 K) the average EF was 4.3-fold. Upon increasing the temperature to 250 K the EF increases to 84-fold. Single complexes show even higher EFs up to 441.0-fold. At increasing temperatures the different spectral pools of PSI from T. elongatus become distinguishable. These pools are affected differently by the plasmonic interactions and show different enhancements. The remarkable increase of the EFs is explained by a rate model including the temperature dependence of the fluorescence yield of PSI and the spectral overlap between absorption and emission spectra of AuNPs and PSI, respectively.