N-Type Coating of Single-Walled Carbon Nanotubes by Polydopamine-Mediated Nickel Metallization.

Single-walled carbon nanotubes (SWCNTs) have unique thermal and electrical properties. Coating them with a thin metal layer can provide promising materials for many applications. This study presents a bio-inspired, environmentally friendly technique for CNT metallization using polydopamine (PDA) as an adhesion promoter, followed by electroless plating with nickel. To improve the dispersion in the aqueous reaction baths, part of the SWCNTs was oxidized prior to PDA coating. The SWCNTs were studied before and after PDA deposition and metallization by scanning and transmission electron microscopy, scanning force microscopy, and X-ray photoelectron spectroscopy. These methods verified the successful coating and revealed that the distribution of PDA and nickel was significantly improved by the prior oxidation step. Thermoelectric characterization showed that the PDA layer acted as a p-dopant, increasing the Seebeck coefficient S of the SWCNTs. The subsequent metallization decreased S, but no negative S-values were reached. Both coatings affected the volume conductivity and the power factor, too. Thus, electroless metallization of oxidized and PDA-coated SWCNTs is a suitable method to create a homogeneous metal layer and to adjust their conduction type, but more work is necessary to optimize the thermoelectric properties.

Oxidative Polymerization of 3,4-Dihydroxybenzylamine─The Lower Homolog of Dopamine.

Polydopamine (PDA) formed by oxidative polymerization of dopamine has attracted wide interest because of its unique properties, in particular its strong adhesion to almost all types of surfaces. 3,4-Dihydroxybenzylamine (DHBA) as the lower homolog of PDA also contains a catechol unit and an amino group and thus can be expected to exhibit a similar adhesion and reaction behavior. In fact, autoxidation of DHBA with air in 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) buffer gives rise to deeply colored oligomer/polymer products (poly(3,4-dihydroxybenzylamine) (PDHBA)) that strongly adhere to several surfaces. Here, the material is characterized by solid-state NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR) spectroscopy, mass spectrometry, and atomic force microscopy (AFM). Reaction pathways were rationalized taking into consideration the analytical results that show similarity to PDA chemistry, but also considering differences, leading to a more complex reaction behavior and thus to new structures not found in PDA.

Analysis of riboflavin/ultraviolet a corneal cross-linking by molecular spectroscopy.

Corneal cross-linking (CXL) with riboflavin and ultraviolet A light is a therapeutic procedure to restore the mechanical stability of corneal tissue. The treatment method is applied to pathological tissue, such as keratoconus and induces the formation of new cross-links. At present, the molecular mechanisms of induced cross-linking are still not known exactly. In this study, we investigated molecular alterations within porcine cornea tissue after treatment with riboflavin and ultraviolet A light by surface enhanced Raman spectroscopy (SERS). For that purpose, after CXL treatment a thin silver layer was vapor-deposited onto cornea flaps. To explore molecular alterations induced by the photochemical process hierarchical cluster analysis (HCA) was used. The detailed analysis of SERS spectra reveals that there is no general change in collagen secondary structure while modifications on amino acid side chains are the most dominant outcome. The formation of secondary and aromatic amine groups as well as methylene and carbonyl groups were observed. Even though successful cross-linking could not be registered in all treated samples, Raman signals of newly formed chemical groups are already present in riboflavin only treated corneas.

Dopamine-Supported Metallization of Polyolefins─A Contribution to Transfer to an Eco-friendly and Efficient Technological Process.

Metallization is a common method to produce functional or decorative coatings on plastic surfaces. State-of-the-art technologies require energy-intensive process steps and the use of organic solvents or hazardous substances to achieve sufficient adhesion between the polymer and the metal layer. The present study introduces a facile bio-inspired "green" approach to improve this technology: the use of dopamine, a small-molecule mimic of the main structural component of adhesive mussel proteins, as an adhesion promoter. To understand dopamine adhesion and identify conditions for successful metallization, polyethylene surfaces were dip-coated with dopamine and metallized with nickel by electroless metallization; essential parameters such as temperature, pH value, concentration of dopamine and buffer, and the deposition time were systematically varied. Effects of adding oxidants to the dopamine bath, cross-linking, thermal and UV post-treatment of the polydopamine film, and plasma pretreatment of the substrate were investigated. The properties of the polydopamine layer and the quality of the metal film were studied by physico-chemical, optical, and mechanical techniques. It was shown that simple dip-coating of the substrate with dopamine under optimal conditions is sufficient to support metal layers with a good optical quality. Technologically relevant metal layer quality and adhesion were obtained with annealed and UV-treated polydopamine films and enhanced by plasma pretreatment of the substrate. The study shows that dopamine provides a new interfacial design for plastic metallization that can reduce energy consumption, use of hazardous substances, and reject rate during manufacturing. The results are essential findings for further technological developments of a universal platform to promote adhesion between plastics and metal or potentially also other material classes, enabling economic material development and more eco-friendly applications.

Bioinspired Polydopamine Coating as an Adhesion Enhancer Between Paraffin Microcapsules and an Epoxy Matrix.

Microencapsulated phase change materials (PCMs) are attracting increasing attention as functional fillers in polymer matrices, to produce smart thermoregulating composites for applications in thermal energy storage (TES) and thermal management. In a polymer composite, the filler-matrix interfacial adhesion plays a fundamental role in the thermomechanical properties. Hence, this work aims to modify the surface of commercial PCM microcapsules through the formation of a layer of polydopamine (PDA), a bioinspired polymer that is emerging as a powerful tool to functionalize chemically inert surfaces due to its versatility and great adhesive potential in many different materials. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) evidenced that after PDA coating, the surface roughness increased from 9 to 86 nm, which is beneficial, as it allows a further increase in the interfacial interaction by mechanical interlocking. Spectroscopic techniques allowed investigating the surface chemistry and identifying reactive functional groups of the PDA layer and highlighted that, unlike the uncoated microcapsules, the PDA layer is able to react with oxirane groups, thereby forming a covalent bond with the epoxy matrix. Hot-stage optical microscopy and differential scanning calorimetry (DSC) highlighted that the PDA modification does not hinder the melting/crystallization process of the paraffinic core. Finally, SEM micrographs of the cryofracture surface of epoxy composites containing neat or PDA-modified microcapsules clearly evidenced improved adhesion between the capsule shell and the epoxy matrix. These results showed that PDA is a suitable coating material with considerable potential for increasing the interfacial adhesion between an epoxy matrix and polymer microcapsules with low surface reactivity. This is remarkably important not only for this specific application but also for other classes of composite materials. Future studies will investigate how the deposition parameters affect the morphology, roughness, and thickness of the PDA layer and how the layer properties influence the capsule-matrix adhesion.

Elucidating the Chemistry behind the Reduction of Graphene Oxide Using a Green Approach with Polydopamine.

A new approach using X-ray photoelectron spectroscopy (XPS) was employed to give insight into the reduction of graphene oxide (GO) using a green approach with polydopamine (PDA). In this approach, the number of carbon atoms bonded to OH and to nitrogen in PDA is considered and compared to the total intensity of the signal resulting from OH groups in polydopamine-reduced graphene oxide (PDA-GO) to show the reduction. For this purpose, GO and PDA-GO with different times of reduction were prepared and characterized by Raman Spectroscopy and XPS. The PDA layer was removed to prepare reduced graphene oxide (RGO) and the effect of all chemical treatments on the thermal and electrical properties of the materials was studied. The results show that the complete reduction of the OH groups in GO occurred after 180 min of reaction. It was also concluded that Raman spectroscopy is not well suited to determine if the reduction and restoration of the sp2 structure occurred. Moreover, a significant change in the thermal stability was not observed with the chemical treatments. Finally, the electrical powder conductivity decreased after reduction with PDA, increasing again after its removal.

Inductive Heating Using a High-Magnetic-Field Pulse to Initiate Chemical Reactions to Generate Composite Materials.

Induction heating is efficient, precise, cost-effective, and clean. The heating process is coupled to an electrically conducting material, usually a metal. As most polymers are dielectric and non-conducting, induction heating is not applicable. In order to transfer energy from an electromagnetic field into polymer induction structures, conducting materials or materials that absorb the radiation are required. This report gives a brief overview of induction heating processes used in polymer technology. In contrast to metals, most polymer materials are not affected by electromagnetic fields. However, an unwanted temperature rise of the polymer can occur when a radio frequency field is applied. The now available high-field magnetic sources provide a new platform for induction heating at very low frequencies, avoiding unwanted thermal effects within the material. Using polycarbonate and octadecylamine as an example, it is demonstrated that induction heating performed by a magnetic-field pulse with a maximum flux density of 59 T can be used to initiate chemical reactions. A 50 nm thick Ag loop, with a mean diameter of 7 mm, placed in the polymer-polymer interface acts as susceptor and a resistive heating element. The formation of urethane as a linker compound was examined by infrared spectroscopic imaging and differential scanning calorimetry.

Label free molecular sexing of monomorphic birds using infrared spectroscopic imaging.

The absence of sexual dimorphism in many birds often makes sex determination difficult. In particular immature birds and adults of monomorphic species show no external sex characteristics. Molecular techniques based on DNA hybridization or polymerase chain reaction (PCR) are standard methods for sex identification. However, these methods are expensive and time consuming procedures and require special sample preparation. Noninvasive methods for a rapid determination of bird's gender are of increasing importance for ornithologists, breeders as well as for successful captive-breeding programs. Fourier transform infrared (FT-IR) spectroscopy is one such technique that can provide gender specific information. In this study, using the example of domestic pigeons (Columba livia f. dom.) we demonstrate that only a small amount of the feather pulp is needed to determine the gender. FT-IR spectroscopic images of feather pulp suspensions were recorded in transmission mode. Principal component analysis (PCA) and linear discriminant analysis (LDA) were performed to identify the sex. The gender related information are described by 2nd and 4th principal component principle component (PC). The 2nd PC represents different amounts of proteins while the 4th PC shows variations within the amide I and amide II bands as well as in the region of phosphate vibrations of nucleic acids. Blood cells of male pigeons exhibit a significantly higher amount of proteins and nucleic acids than those of female pigeons. Feather pulp samples of male species were assigned with 100% accuracy. Seven from eight female samples were assigned correctly while one sample could not be classified. This study demonstrates that the sex of domestic pigeons can be accurately and and rapidly identified by infrared spectroscopic imaging.

Characterization of metal-supported poly(methyl methacrylate) microstructures by FTIR imaging spectroscopy.

Thin microstructured poly(methyl methacrylate) (PMMA) films may be used as scaffolds for biosensor arrays. Microstructured pores form miniaturized vessels, each constituting an individual reaction vessel or detector element. Arrays of micropores with diameters between 2 and 80 microm were prepared in thin PMMA films on gold by optical lithography. Laterally resolved chemical information for microstructured PMMA films on a gold substrate was obtained by FTIR spectroscopic imaging. The carbonyl band was used to characterize the microstructure. Spectroscopic results indicate small amounts of PMMA residues inside the pores. A downshift of 5 cm(-1) compared to the position of the PMMA bulk carbonyl band indicates interactions of the PMMA residue with the gold substrate. Additional small bands are observed which indicate the formation of carboxylate during PMMA microstructuring. Three possible types of strong PMMA-gold interactions are discussed. All strong PMMA-gold interactions involve carbonyl or carboxyl oxygen.