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Polymeric materials modified with tertiary amino groups exhibit attractive properties for use in aqueous environments. Ring-opening metathesis polymerization (ROMP) is one of the versatile tools to...

A series of variants of antithrombogenic poly(2-methoxyethyl acrylate) with controlled side-chain spacing were prepared via regio-selective ring-opening metathesis polymerization. In general, under...

Several recent studies on compressive video sensing realized scene capture beyond the fundamental trade-off limit between spatial resolution and temporal resolution using random space-time sampling. However, most of these studies obtained results for higher-frame-rate video that was produced in simulation experiments or using an optically simulated random sampling camera, because there are currently no commercially available image sensors with random exposure or sampling capabilities. We fabricated a prototype complementary metal-oxide-semiconductor (CMOS) image sensor with quasi pixel-wise exposure timing that can realize nonuniform space-time sampling. The prototype sensor resets exposures independently by columns and fixes these exposures by rows for each 8 × 8-pixel block. This CMOS sensor is not fully controllable the pixels and has line-dependent control, but offers greater flexibility when compared with regular CMOS or charge-coupled device sensors with global or rolling shutters. We propose a method of realizing pseudo-random sampling for high-speed video acquisition that uses the flexibility of the CMOS sensor. We reconstruct the high-speed video sequence from images produced in pseudo-random sampling using a pre-learned decoder.

Modifying the side chain of poly(meth)acrylate with moieties originating from biocompatible polymers can be an effective method for developing novel blood-compatible polymers. Inspired by biocompatible poly(2-methyl-2-oxazoline) (PMeOx) and poly(2-ethyl-2-oxazoline) (PEtOx), four water-soluble poly(tertiary amide acylate) analogues bearing a pendant tertiary amide were synthesized. The results of hemolysis and cell viability tests showed that all the poly(tertiary amide acylate) analogues were compatible with red blood cells, HeLa cells, and normal human dermal fibroblasts as PMeOx or PEtOx. Among the four poly(tertiary amide acylate) analogues, poly[2-(N-methylpropionamido)ethyl acrylate] (PPEA) and poly[2-(N-ethylacetamido)ethyl acrylate] (PEAE) showed thermosensitivity in aqueous solution; especially, PPEA (10 mg mL-1) exhibited a lower critical solution temperature of 37 °C. Water-insoluble copolymers were prepared to investigate the possibility of applying these synthesized polymers as blood-compatible coatings. The poly[n-butyl methacrylate70-co-2-(N-methylacetamido)ethyl methacrylate30] (coPAEM) coatings significantly suppressed plasma protein adsorption, denaturation degree of adsorbed fibrinogen, and platelet adhesion. Intermediate water (IW), whose content can generally indicate the blood compatibility of polymers, was found in all hydrated homopolymers and copolymers by differential scanning calorimetry. The present work demonstrated that the tertiary amide moiety in the side chain of poly(meth)acrylate was an effective contributor to blood compatibility and IW.

Hydration states of polymers are known to directly influence the adsorption of biomolecules. Particularly, intermediate water (IW) has been found able to prevent protein adsorption. Experimental studies have examined the IW content and nonthrombogenicity of poly(2-methoxyethyl acrylate) analogues with different side-chain spacings and lengths, which are HPx (x is the number of backbone carbons in a monomer) and PMCyA (y is the number of carbons in-between ester and ether oxygens of the side-chain) series, respectively. HPx was reported to possess more IW content but lower nonthrombogenicity compared to PMCyA with analogous composition. To understand the reason for the conflict, molecular dynamics simulations were conducted to elucidate the difference in the properties between the HPx and PMCyA. Simulation results showed that the presence of more methylene groups in the side chain more effectively prohibits water penetration in the polymer than those in the polymer backbone, causing a lower IW content in the PMCyA. At a high water content, the methoxy oxygen in the shorter side chain of the HPx cannot effectively bind water compared to that in the PMCyA side chain. HPx side chains may have more room to contact with molecules other than water (e.g., proteins), causing experimentally less nonthrombogenicity of HPx than that of PMCyA. In summary, theoretical simulations successfully explained the difference in the effects of side-chain spacing and length in atomistic scale.

Intermediate water (IW) has been reported to play an important role in nonthrombogenicity of biomaterials. However, clear insights into the IW in the hydrated polymer are still debated. In this study, a series of molecular dynamics simulations was performed to identify the IW structure in hydrated poly(ω-methoxyalkyl acrylate)s (PMCxAs, where x indicates the number of methylene carbons) with x = 1-6. Through the quantitative comparison with experimental measurements, IW molecules were suggested to mainly come from the water interacting with an oxygen atom of the polymers, while most of the nonfreezing water (NFW) molecules corresponded to the water interacting with two polymer oxygen atoms. In addition, the IW molecules were found to effectively enhance the flexibility of the PMCxA side chains in comparison with the NFW molecules. The variations of the saturated IW content and the side-chain flexibility with the methylene carbon chain length of PMCxA were also found to be correlated with the experimental nonthrombogenicity of PMCxA, suggesting that the polymer with the more saturated IW content and higher chain flexibility possesses better nonthrombogenicity. Furthermore, through the analyses of the interplays between the IW and polymer and between IW and its adjacent water, we found that the presence of the unique interaction between IW and its adjacent water in the hydrated poly(2-methoxyethyl acrylate) (PMEA) is the main factor causing different cold crystallization behaviors of PMEA from the other PMCxAs rather than the interaction between water and the PMCxA matrix. The findings will be useful in the development of new nonthrombogenic materials.

Intermediate water (IW) is known to play an important role in the antifouling property of biocompatible polymers. However, how IW prevents protein adsorption is still unclear. To understand the role of IW in the antifouling mechanism, molecular dynamics simulation was used to investigate the dynamic properties of water and side-chains for hydrated poly(ω-methoxyalkyl acrylate)s (PMCxA, where x indicates the number of methylene carbons) with x = 1-6 and poly(n-butyl acrylate) (PBA) in this study. Since the polymers uptake more water than their equilibrium water content (EWC) at the polymer/water interface, we analyzed the hydrated polymers at a water content higher than that of EWC. It was found that the water molecules interacting with one polymer oxygen atom (BW1), of which most are IW molecules, in PMC2A exhibit the lowest mobility, while those in PBA and PMC1A show a higher mobility. The result was consistent with the expectation that the biocompatible polymer with a long-resident hydration layer possesses good antifouling property. Through the detailed analysis of side-chain binding with three different types of BW1 molecules, we found that the amount of side-chains simultaneously interacting with two BW1 molecules, which exhibit the highest flexibility among the three kinds of side-chains, is the lowest for PMC1A. The high mobility of BW1 is thus suggested as the main factor for the poor protein adsorption resistance of PMC1A even though it possesses enough IW content and relatively flexible side-chains. Contrarily, a maximum amount of side-chains simultaneously interacting with two BW1 molecules was found in the hydrated PMC3A. The moderate side-chain length of PMC3A allows side-chains to simultaneously interact with two BW1 molecules and minimizes the hydrophobic part attractively interacting with a protein at the polymer/water interface. The unique structure of PMC3A may be the reason causing the best protein adsorption resistance among the PMCxAs.

The blood-compatible polymer poly(2-methoxyethyl acrylate) (PMEA) is composed of nanometer-scale interfacial structures because of the phase separation of the polymer and water at the PMEA/phosphate-buffered saline (PBS) interface. We synthesized PMEA with four different molecular weights (19, 30, 44, and 183 kg/mol) to investigate the effect of the molecular weight on the interfacial structures and blood compatibility. The amounts of intermediate water and fibrinogen adsorption were not affected by the molecular weight of PMEA. In contrast, the degree of denaturation of adsorbed fibrinogen molecules and platelet adhesion increased as the molecular weight increased. Atomic force microscopy observation revealed that the domain size of the microphase separation structures observed at the PMEA/PBS interfaces drastically (nearly 3 times in the mean area of a domain) changed with the molecular weight. PMEA with a lower molecular weight showed a smaller polymer-rich domain size, as expected on the basis of the microphase separation of polymer-rich and water-rich domains. The small domain size suppressed the aggregation and denaturation of adsorbed fibrinogen molecules because only a few fibrinogen molecules were adsorbed on a domain. Increasing the domain size enhanced the denaturation of adsorbed fibrinogen molecules. Controlling the interfacial structures is crucial for ensuring the blood compatibility of polymer interfaces.

The practical use of the viscous liquid polymer, poly(2-methoxyethyl acrylate) (PMEA), was expanded from thin films with excellent blood compatibility to thick coatings and free-standing films without essentially sacrificing its blood compatibility. This was undertaken by creating multiple hydrogen-bonding polymer networks by introducing a functional methacrylic monomer bearing a 6-methyl-2-ureido-4[1H]-pyrimidone group in the PMEA backbone via free radical copolymerization. The hydrogen-bonded PMEA (H-PMEA) contained about 6 mol % of the functional monomer in the copolymer. These functional monomers as physical cross-links are distributed in the PMEA matrix with a Tg of −35 °C, making H-PMEA a solid rubber-like material with recoverable tensile strain. Additionally, mechanical tests revealed its tensile strength, and thermogravimetric analyses confirmed its higher thermostability. The dry and hydration states of H-PMEA were assessed by differential scanning calorimetry, contact angle, and atomic force microscopy measurements. Comparison with viscous PMEA was made. For the first time, we included PVC alongside PET, the surface we usually use as a negative control, in the platelet adhesion test with human blood, and found out that 1.5 times more platelets adhered onto the PVC surface than onto the PET surface, while H-PMEA proved to have a clear edge. Thus, H-PMEA may serve as a suitable replacement for polymers in products contacting blood as it shows potential for making free-standing films, thick coatings, implants, and articles with various geometries for the medicinal industry.

Most conventional digital video cameras face a fundamental trade-off between spatial resolution, temporal resolution and dynamic range (i.e., brightness resolution) because of a limited bandwidth for data transmission. A few recent studies have shown that with non-uniform space-time sampling, such as that implemented with pixel-wise coded exposure, one can go beyond this trade-off and achieve high efficiency for scene capture. However, in these studies, the sampling schemes were pre-defined and independent of the target scene content. In this paper, we propose an adaptive space-time-brightness sampling method to further improve the efficiency of video capture. The proposed method adaptively updates a pixel-wise coded exposure pattern using the information analyzed from previously captured frames. We built a prototype camera that enables adaptive coding of patterns online to show the feasibility of the proposed adaptive coded exposure method. Simulation and experimental results show that the adaptive space-time-brightness sampling scheme achieves more accurate video reconstruction results and high dynamic range with less computational cost, than previous method. To the best of our knowledge, our prototype is the first implementation of an adaptive pixel-wise coded exposure camera.

A light field, which is often understood as a set of dense multi-view images, has been utilized in various 2D/3D applications. Efficient light field acquisition using a coded aperture camera is the target problem considered in this paper. Specifically, the entire light field, which consists of many images, should be reconstructed from only a few images that are captured through different aperture patterns. In previous work, this problem has often been discussed from the context of compressed sensing (CS). In contrast, we formulated this problem from the perspective of principal component analysis (PCA) to derive optimal non-negative aperture patterns and a straight-forward reconstruction algorithm. Even though it is based on a conventional technique, our method has proven to be more accurate and much faster than a state-of-the-art CS-based method.

Several recent studies in compressive video sensing have realized scene capture beyond the fundamental trade-off limit between spatial resolution and temporal resolution using random space-time sampling. However, most of these studies showed results for higher frame rate video that were produced by simulation experiments or using an optically simulated random sampling camera, because there are currently no commercially available image sensors with random exposure or sampling capabilities. We fabricated a prototype complementary metal oxide semiconductor (CMOS) image sensor with quasi pixel-wise exposure timing that can realize nonuniform space-time sampling. The prototype sensor can reset exposures independently by columns and fix these amount of exposure by rows for each 8×8 pixel block. This CMOS sensor is not fully controllable via the pixels, and has line-dependent controls, but it offers flexibility when compared with regular CMOS or charge-coupled device sensors with global or rolling shutters. We propose a method to realize pseudo-random sampling for high-speed video acquisition that uses the flexibility of the CMOS sensor. We reconstruct the high-speed video sequence from the images produced by pseudo-random sampling using an over-complete dictionary. The proposed method also removes the rolling shutter effect from the reconstructed video.