Institute of Polymers

Experiments and basic Physics of exciton diffusion in organic semiconductors are reviewed.

Organic microcrystals ranging from several tens nm to µm in size of several chromophores were successfully prepared by simply dispersing ethanol solutions of compounds into stirred water, i.e. by a reprecipitation method. The size of microcrystals was found to depend on concentration of ethanol solutions, dispersing conditions, temperature and so on.

What can stop the mountain of discarded plastic packaging from growing? One solution to be considered is the development and use of biodegradable polymers. The advantages and drawbacks of various biodegradable plastics, water‐soluble polymers, and natural and semisynthetic polymers are outlined in tis review. The Figure shows a fork made of ECO‐PLA, which is based on poly(lactic acid), after 33 days of degradation. magnified image

We have demonstrated a novel sensing strategy employing single-stranded probe DNA, unmodified gold nanoparticles, and a positively charged, water-soluble conjugated polyelectrolyte to detect a broad range of targets including nucleic acid (DNA) sequences, proteins, small molecules, and inorganic ions. This nearly "universal" biosensor approach is based on the observation that, while the conjugated polyelectrolyte specifically inhibits the ability of single-stranded DNA to prevent the aggregation of gold-nanoparticles, no such inhibition is observed with double-stranded or otherwise "folded" DNA structures. Colorimetric assays employing this mechanism for the detection of hybridization are sensitive and convenient--picomolar concentrations of target DNA are readily detected with the naked eye, and the sensor works even when challenged with complex sample matrices such as blood serum. Likewise, by employing the binding-induced folding or association of aptamers we have generalized the approach to the specific and convenient detection of proteins, small molecules, and inorganic ions. Finally, this new biosensor approach is quite straightforward and can be completed in minutes without significant equipment or training overhead.

Heteroatom-doped carbon dots (CDs), due to their excellent photoluminescence (PL) properties, attracted widespread attention recently and demonstrated immense promise for diverse applications, particularly for biological applications. The objective of this feature article is to provide a comprehensive overview of the recent progress in the research and development of heteroatom-doped CDs and a detailed description of the influence of single or co-doping heteroatoms on their PL behavior. The most recent understanding and critical insights into the PL mechanism of heteroatom-doped CDs are also highlighted. Moreover, potential bio-related applications of heteroatom-doped CDs in biosensing, bioimaging, and theranostics are also reviewed. This state-of-the-art review will provide a platform for understanding the intricate details of heteroatom-doped CDs, a summary of the latest progress in the field, and related applications in biology and is expected to inspire further developments in this exciting class of materials.

Transparent sheets of epoxy resin reinforced with nylon-4,6 nanofibers are described. The 30–200 nm diameter fibers, obtained by electrospinning from formic acid solutions, are reported to provide significant improvement in strength and stiffness to the epoxy film. The Figure is a scanning electron microscopy image of the electrospun nanofibers.

The recent progress, challenges and promising future of design and synthesis of inks and device fabrication by inkjet printing are reviewed and discussed.

Natural and synthetic polymers are a versatile platform for developing biomaterials in the biomedical and environmental fields. Natural polymers are organic compounds that are found in nature. The most common natural polymers include polysaccharides, such as alginate, hyaluronic acid, and starch, proteins, e.g., collagen, silk, and fibrin, and bacterial polyesters. Natural polymers have already been applied in numerous sectors, such as carriers for drug delivery, tissue engineering, stem cell morphogenesis, wound healing, regenerative medicine, food packaging, etc. Various synthetic polymers, including poly(lactic acid), poly(acrylic acid), poly(vinyl alcohol), polyethylene glycol, etc., are biocompatible and biodegradable; therefore, they are studied and applied in controlled drug release systems, nano-carriers, tissue engineering, dispersion of bacterial biofilms, gene delivery systems, bio-ink in 3D-printing, textiles in medicine, agriculture, heavy metals removal, and food packaging. In the following review, recent advancements in polymer chemistry, which enable the imparting of specific biomedical functions of polymers, will be discussed in detail, including antiviral, anticancer, and antimicrobial activities. This work contains the authors' experimental contributions to biomedical and environmental polymer applications. This review is a vast overview of natural and synthetic polymers used in biomedical and environmental fields, polymer synthesis, and isolation methods, critically assessessing their advantages, limitations, and prospects.

The pathogenicity of influenza virus infection in the mice involves, at least in part, overreaction of the immune responses of the host rather than a direct effect of virus multiplication. Xanthine oxidase, which is responsible for the generation of oxygen free radicals, was elevated in serum and lung tissue of mice infected with influenza virus. To test the theory that oxygen-free radicals are involved in pathogenesis, free radicals were removed by injecting superoxide dismutase (SOD), a specific superoxide radical scavenger, which was conjugated with a pyran copolymer. The conjugate protected mice against a potentially lethal influenza virus infection if administered 5 to 8 days after infection. These findings indicate that oxygen radicals are important in the pathogenesis of influenza virus infection, and that a polymer-conjugated SOD has therapeutic potential for this virus infection and other diseases associated with free radicals.

Simple spectrophotometric method for the estimation of accessible amino groups and preparation of polyurethane nanocomposites.

Glutaraldehyde crosslinking of native or reconstituted collagen fibrils and tissues rich in collagen significantly reduces biodegradation. Other aldehydes are less efficient than glutaraldehyde in generating chemically, biologically, and thermally stable crosslinks. Tissues crosslinked with glutaraldehyde retain many of the viscoelastic properties of the native collagen fibrillar network which render them suitable for bioprostheses. Implants of collagenous materials crosslinked with glutaraldehyde are subject long-term to calcification, biodegradation, and low-grade immune reactions. We have attempted to overcome these problems by enhancing crosslinking through bridging of activated carboxyl groups with diamines and using glutaraldehyde to crosslink the epsilon-NH2 groups in collagen and the unreacted amines introduced by aliphatic diamines. This crosslinking reduces tissue degradation and nearly eliminates humoral antibody induction. Covalent binding of diphosphonates, specifically 3-amino-1-hydroxypropane-1, 1-diphosphonic acid (3-APD), and chondroitin sulfate to collagen or to the crosslink-enhanced collagen network reduces its potential for calcification. Platelet aggregation is also reduced by glutaraldehyde crosslinking and nearly eliminated by the covalent binding of chondroitin sulfate to collagen. The cytotoxicity of residual glutaraldehyde--leaching through the interstices of the collagen fibrils or the tissue matrix--and of reactive aldehydes associated with the bound polymeric glutaraldehyde can be minimized by neutralization and thorough rinsing after crosslinking and storage in a nontoxic bacteriostatic solution.

Recent advances in emerging Janus two-dimensional materials including fundamental physics, unique properties and potential device applications are reviewed.

This review summarizes recent advances in the science and applications of conjugated polyelectrolytes (CPEs), with an emphasis on direct visual sensing, cellular imaging, and the fabrication of optoelectronic devices. CPEs backbones that incorporate donor−acceptor units are useful for direct visual sensing, whereas CPEs with hyperbranched structures, or biocompatible long side chains, are particularly useful for cellular imaging. With specially designed counterions, CPEs also demonstrate unique function in device fabrication and operation, for example, in dye-sensitized solar cells (DSSCs), bulk heterojunction (BHJ) solar cells, polymer light-emitting diodes (PLEDs), polymer light-emitting electrochemical cells (PLECs), and organic thin film transistors (OFET). Additionally, new strategies to modify and optimize CPE properties for specific applications are provided. The work summarized herein not only illustrates relationships between molecular structures and function, but also highlights how the structural versatility of CPEs makes them a unique category of multifunctional materials with the potential for fulfilling a variety of optical and electronic applications in solution, mixed media, and in the solid state.

Abstract Several methods are compared for preparing collagen‐glycosaminoglycan (GAG) membranes of high or low porosity. Collagen‐GAG membranes have been used to cover satisfactorily large experimental full‐thickness skin wounds in guinea pigs over the past few years. Methods studies as means for controlling pore size are confined to purely physical processes which do not require use of additives or chemical reagents to form the porous membrane. We find that membranes, initially swollen in distilled water or saline, shrink linearly to no less than 94% of original dimension after freeze drying; to 75% after critical point drying (from CO 2 , following water‐ethanol exchange); and to 41% of original dimension following air drying from the swollen state. Scanning electron microscopic study of the pore structure resulting from each drying procedure confirms our major conclusion: A carefully designed freeze drying process, two variants of which are described in detail, yields membranes with the highest mean pore size, as measured by quantitative stereological procedures. Critical point drying gave significantly more shrinkage and a lower mean pore size than either one of the two freeze drying procedures used.

Abstract The circular dichroism spectra of β-cyclodextrin complexes with naphthalene derivatives were investigated. A remarkable difference in the spectra was observed between the 1-substituted naphthalene complex and the 2-substituted naphthalene complex, indicating that the steric effect of substituents on the formation of the complex is so strong that the structures may be different for these complexes. The calculation of the rotational strength by the method of Kirkwood-Tinoco revealed that the structure of the 2-substituted naphthalene complex is an axial inclusion.

The self-assembly of inorganic nanoparticles is of great importance in realizing their enormous potentials for broad applications due to the advanced collective properties of nanoparticle ensembles. Various molecular ligands (e.g., small molecules, DNAs, proteins, and polymers) have been used to assist the organization of inorganic nanoparticles into functional structures at different hierarchical levels. Among others, polymers are particularly attractive for use in nanoparticle assembly, because of the complex architectures and rich functionalities of assembled structures enabled by polymers. Polymer-guided assembly of nanoparticles has emerged as a powerful route to fabricate functional materials with desired mechanical, optical, electronic or magnetic properties for a broad range of applications such as sensing, nanomedicine, catalysis, energy storage/conversion, data storage, electronics and photonics. In this review article, we summarize recent advances in the polymer-guided self-assembly of inorganic nanoparticles in both bulk thin films and solution, with an emphasis on the role of polymers in the assembly process and functions of resulting nanostructures. Precise control over the location/arrangement, interparticle interaction, and packing of inorganic nanoparticles at various scales are highlighted.

Summary Thermal modification of wood produces a wood material with many interesting properties, such as enhanced dimensional stability, lower equilibrium moisture content and increased biological durability. Changes in the chemical structure of pine ( Pinus sylvestris ) caused by thermal treatment were investigated by studying various components of wood using 13 C CPMAS NMR spectroscopy. Electron spin resonance (ESR) spectroscopy on the same set of samples was used to study the formation and stability of free radicals formed during the treatment. The most remarkable changes revealed by solid state NMR were the increase in relative crystallinity of cellulose and destruction and deacetylation of hemicelluloses. Changes in the lignin fraction were mostly registered as diminishment in the methoxyl content, although the intensity of the aromatic region increased relative to the carbohydrate fraction during the treatment. Increase in the intensities of the ESR signals from thermally treated wood samples proves the formation of stable free radicals. In addition, radical formation is believed to take part in condensation reactions leading to crosslinks within the lignin and possibly between lignin and other wood components. Both of the methods used indicate that the changes are most remarkable when the treatment temperature is over 200°C.

A critical aspect in the development of biomaterials is the optimization of their surface properties to achieve an adequate cell response. In the present work, electrospun polycaprolactone nanofiber meshes (NFMs) are treated by radio-frequency (RF) plasma using different gases (Ar or O(2)), power (20 or 30 W), and exposure time (5 or 10 min). Morphological and roughness analysis show topographical changes on the plasma-treated NFMs. X-ray photoelectron spectroscopy (XPS) results indicate an increment of the oxygen-containing groups, mainly --OH and --C==O, at the plasma-treated surfaces. Accordingly, the glycerol contact angle results demonstrate a decrease in the hydrophobicity of plasma-treated meshes, particularly in the O(2)-treated ones. Three model cell lines (fibroblasts, chondrocytes, and osteoblasts) are used to study the effect of plasma treatments over the morphology, cell adhesion, and proliferation. A plasma treatment with O(2) and one with Ar are found to be the most successful for all the studied cell types. The influence of hydrophilicity and roughness of those NFMs on their biological performance is discussed. Despite the often claimed morphological similarity of NFMs to natural extracellular matrixes, their surface properties contribute substantially to the cellular performance and therefore those should be optimized.

This review focuses on the polyesters such as polylactide and polyhydroxyalkonoates, as well as polyamides produced from renewable resources, which are currently among the most promising (bio)degradable polymers. Synthetic pathways, favourable properties and utilisation (most important applications) of these attractive polymer families are outlined. Environmental impact and in particular (bio)degradation of aliphatic polyesters, polyamides and related copolymer structures are described in view of the potential applications in various fields.

Using the CAViaR tool to estimate the value-at-risk (VaR) and the Granger causality risk test to quantify extreme risk spillovers, we propose an extreme risk spillover network for analysing the interconnectedness across financial institutions. We construct extreme risk spillover networks at 1% and 5% risk levels (which we denote 1% and 5% VaR networks) based on the daily returns of 84 publicly listed financial institutions from four sectors—banks, diversified financials, insurance and real estate—during the period 2006–2015. We find that extreme risk spillover networks have a time-lag effect. Both the static and dynamic networks show that on average the real estate and bank sectors are net senders of extreme risk spillovers and the insurance and diversified financials sectors are net recipients, which coheres with the evidence from the recent global financial crisis. The networks during the 2008–2009 financial crisis and the European sovereign debt crisis exhibited distinctive topological features that differed from those in tranquil periods. Our approach supplies new information on the interconnectedness across financial agents that will prove valuable not only to investors and hedge fund managers, but also to regulators and policy-makers.