Virtual Light Sensing Technology for Fast Calculation of Daylight Autonomy Metrics.

Virtual sensing technology uses mathematical calculations instead of natural measurements when the latter are too difficult or expensive. Nowadays, application of virtual light sensing technology becomes almost mandatory for daylight analysis at the stage of architectural project development. Daylight Autonomy metrics should be calculated multiple times during the project. A properly designed building can reduce the necessity of artificial lighting, thus saving energy. There are two main daylight performance metrics: Spatial Daylight Autonomy (sDA) and Annual Sunlight Exposure (ASE). To obtain their values, we have to simulate global illumination for every hour of the year. A light simulation method should therefore be as efficient as possible for processing complex building models. In this paper we present a method for fast calculation of Daylight Autonomy metrics, allowing them to be calculated within a reasonable timescale. We compared our method with straightforward calculations and other existing solutions. This comparison demonstrates good agreement; this proves sufficient accuracy and higher efficiency of the method. Our method also contains an original algorithm for the automatic setting of the sensing area. The sDA metric is calculated considering blinds control, which should open or close them depending on overexposure to direct sunlight. Thus, we developed an optimization procedure to determine the blinds configuration at any time.

XPS Modeling of Immobilized Recombinant Angiogenin and Apoliprotein A1 on Biodegradable Nanofibers.

The immobilization of viable proteins is an important step in engineering efficient scaffolds for regenerative medicine. For example, angiogenin, a vascular growth factor, can be considered a neurotrophic factor, influencing the neurogenesis, viability, and migration of neurons. Angiogenin shows an exceptional combination of angiogenic, neurotrophic, neuroprotective, antibacterial, and antioxidant activities. Therefore, this protein is a promising molecule that can be immobilized on carriers used for tissue engineering, particularly for diseases that are complicated by neurotrophic and vascular disorders. Another highly important and viable protein is apoliprotein A1. Nevertheless, the immobilization of these proteins onto promising biodegradable nanofibers has not been tested before. In this work, we carefully studied the immobilization of human recombinant angiogenin and apoliprotein A1 onto plasma-coated nanofibers. We developed a new methodology for the quantification of the protein density of these proteins using X-ray photoelectron spectroscopy (XPS) and modeled the XPS data for angiogenin and apoliprotein A1 (Apo-A1). These findings were also confirmed by the analysis of immobilized Apo-A1 using fluorescent microscopy. The presented methodology was validated by the analysis of fibronectin on the surface of plasma-coated poly(ε-caprolactone) (PCL) nanofibers. This methodology can be expanded for other proteins and it should help to quantify the density of proteins on surfaces using routine XPS data treatment.

Plasma-Coated Polycaprolactone Nanofibers with Covalently Bonded Platelet-Rich Plasma Enhance Adhesion and Growth of Human Fibroblasts.

Biodegradable nanofibers are extensively employed in different areas of biology and medicine, particularly in tissue engineering. The electrospun polycaprolactone (PCL) nanofibers are attracting growing interest due to their good mechanical properties and a low-cost structure similar to the extracellular matrix. However, the unmodified PCL nanofibers exhibit an inert surface, hindering cell adhesion and negatively affecting their further fate. The employment of PCL nanofibrous scaffolds for wound healing requires a certain modification of the PCL surface. In this work, the morphology of PCL nanofibers is optimized by the careful tuning of electrospinning parameters. It is shown that the modification of the PCL nanofibers with the COOH plasma polymers and the subsequent binding of NH2 groups of protein molecules is a rather simple and technologically accessible procedure allowing the adhesion, early spreading, and growth of human fibroblasts to be boosted. The behavior of fibroblasts on the modified PCL surface was found to be very different when compared to the previously studied cultivation of mesenchymal stem cells on the PCL nanofibrous meshes. It is demonstrated by X-ray photoelectron spectroscopy (XPS) that the freeze-thawed platelet-rich plasma (PRP) immobilization can be performed via covalent and non-covalent bonding and that it does not affect biological activity. The covalently bound components of PRP considerably reduce the fibroblast apoptosis and increase the cell proliferation in comparison to the unmodified PCL nanofibers or the PCL nanofibers with non-covalent bonding of PRP. The reported research findings reveal the potential of PCL matrices for application in tissue engineering, while the plasma modification with COOH groups and their subsequent covalent binding with proteins expand this potential even further. The use of such matrices with covalently immobilized PRP for wound healing leads to prolonged biological activity of the immobilized molecules and protects these biomolecules from the aggressive media of the wound.

Analysis of epoxy functionalized layers synthesized by plasma polymerization of allyl glycidyl ether.

The deposition of epoxide groups by plasma polymerization opens new horizons for robust and quick immobilization of biomolecules on any type of substrate. However, as of now there are just very few papers dealing with the deposition of epoxy layers by plasma polymerization, probably due to the high reactivity of this group leading to a low functionalization efficiency. In this work we carried out an extensive experimental and theoretical investigation of plasma synthesis of epoxide groups from a low pressure allyl glycydyl ether (AGE) plasma. The influence of composite parameter W/F and the working pressure on the density of epoxide groups and the layer stability was thoroughly addressed. It was found that by increasing the working pressure it is possible to sufficiently raise the concentration of epoxide groups. The composite parameter W/F was shown to be a crucial parameter in affecting the density of epoxides. An optimal value of W/F of around 2.3 eV per molecule leading to the highest density of epoxides produced in the process at 15 Pa was revealed through FT-IR and XPS findings. This value correlates well with the ab initio calculations suggesting that the lowest bond dissociation energy belongs to the C-O bond of the epoxide ring. Therefore, in order to increase the density of epoxides deposited by plasma polymerization, a precursor molecule containing at least two epoxide rings is strongly advised to be employed.

Free-Radical-Induced Grafting from Plasma Polymer Surfaces.

With the advances in science and engineering in the second part of the 20th century, emerging plasma-based technologies continuously find increasing applications in the domain of polymer chemistry, among others. Plasma technologies are predominantly used in two different ways: for the treatment of polymer substrates by a reactive or inert gas aiming at a specific surface functionalization or for the synthesis of a plasma polymer with a unique set of properties from an organic or mixed organic-inorganic precursor. Plasma polymer films (PPFs), often deposited by plasma-enhanced chemical vapor deposition (PECVD), currently attract a great deal of attention. Such films are widely used in various fields for the coating of solid substrates, including membranes, semiconductors, metals, textiles, and polymers, because of a combination of interesting properties such as excellent adhesion, highly cross-linked structures, and the possibility of tuning properties by simply varying the precursor and/or the synthesis parameters. Among the many appealing features of plasma-synthesized and -treated polymers, a highly reactive surface, rich in free radicals arising from deposition/treatment specifics, offers a particular advantage. When handled carefully, these reactive free radicals open doors to the controllable surface functionalization of materials without affecting their bulk properties. The goal of this review is to illustrate the increasing application of plasma-based technologies for tuning the surface properties of polymers, principally through free-radical chemistry.

Free radical generation and concentration in a plasma polymer: the effect of aromaticity.

Plasma polymer films (PPF) have increasing applications in many fields due to the unique combination of properties of this class of materials. Among notable features arising from the specifics of plasma polymerization synthesis, a high surface reactivity can be advantageously used when exploited carefully. It is related to the presence of free radicals generated during the deposition process through manifold molecular bond scissions in the energetic plasma environment. In ambient atmosphere, these radicals undergo autoxidation reactions resulting in undesired polymer aging. However, when the reactivity of surface radicals is preserved and they are put in direct contact with a chemical group of interest, a specific surface functionalization or grafting of polymeric chains can be achieved. Therefore, the control of the surface free radical density of a plasma polymer is crucially important for a successful grafting. The present investigation focuses on the influence of the hydrocarbon precursor type, aromatic vs aliphatic, on the generation and concentration of free radicals on the surface of the PPF. Benzene and cyclohexane were chosen as model precursors. First, in situ FTIR analysis of the plasma phase supplemented by density functional theory calculations allowed the main fragmentation routes of precursor molecules in the discharge to be identified as a function of energy input. Using nitric oxide (NO) chemical labeling in combination with X-ray photoelectron spectroscopy analysis, a quantitative evaluation of concentration of surface free radicals as a function of input power has been assessed for both precursors. Different evolutions of the surface free radical density for the benzene- and cyclohexane-based PPF, namely, a continuous increase versus stabilization to a plateau, are attributed to different plasma polymerization mechanisms and resulting structures as illustrated by PPF characterization findings. The control of surface free radical density can be achieved through the stabilization of radicals due to the proximity of incorporated aromatic rings. Aging tests highlighted the inevitable random oxidation of plasma polymers upon exposure to air and the necessity of free radical preservation for a controlled surface functionalization.

Use of free radicals on the surface of plasma polymer for the initiation of a polymerization reaction.

A novel approach to functionalize plasma polymer films (PPFs) through the grafting polymerization initiated from free radicals trapped in the film was developed in this work. 2-Ethylhexyl acrylate (EHA) was chosen as radically polymerizable monomer given the wide use of its corresponding polymer in coating and adhesive applications. The occurrence of the grafting was first confirmed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). Then grafted chains were studied in more detail. The thickness of grafted chains was quantitatively estimated by angle-resolved XPS (ARXPS), while their morphology and interfacial behavior were qualitatively investigated by atomic force microscopy (AFM), contact angle measurements, and quartz crystal microbalance (QCM). The latter technique provided additional insights regarding the swelling behavior of the grafted layer and its stability upon exposure to challenging environments. Reported scientific findings suggest to use this approach for the covalent binding of a very thin layer on the top surface of a PPF without affecting its bulk properties.