Functional Organic Polymers Research Articles

Surface Functionalization and Escherichia coli Detection Using Surface-Enhanced Raman Spectroscopy Driven by Functional Organic Polymer/Gold Nanofilm-Based Microfluidic Chip.

In this work, a microfluidic prototype based on polymeric materials was developed to monitor surface processes using surface-enhanced Raman spectroscopy (SERS), keeping the reagents free of environmental contamination. The prototype was fabricated on poly(methyl methacrylic acid) (PMMA). A micrometric membrane of a functional organic polymer (FOP) based on p-terphenyl and bromopyruvic acid monomers was formed on the PMMA surface to promote the formation of metal nanoclusters. Au nanosized film was deposited on the FOP membrane to give rise to the SERS effect. A microchannel was formed on another piece of PMMA using micromachining. A representative 3D model of the prototype layer arrangement was built and simulated in COMSOL Multiphysics® to approximate the electric field distribution and calculate the power enhancement factor as the Au film changes over time. The fabrication process was characterized using UV-visible and Raman spectroscopies and XPS. The prototype was tested using a Raman microscope and liquid solutions of cysteamine and Escherichia coli (E. coli). The simulation results demonstrated that the morphological characteristics of the Au layer give rise to the SERS effect, and the power enhancement factor reaches values as high as 8.8 × 105 on the FOP surface. The characterization results showed the formation of the FOP and the Au film on PMMA and the surface functionalization with amine groups. The Raman spectra of the prototype showed temporal evolution as different compounds were deposited on the upper wall of the microchannel. Characteristic peaks associated with these compounds were detected with continuous monitoring over time. This prototype offers many benefits for applications like monitoring biological processes. Some advantages include timely surface evaluation while avoiding environmental harm, decreased use of reagents and samples, minimal interference with the process by measuring, and detecting microorganisms in just 1 h, as demonstrated with the E. coli sample.

1st Iberian Symposium on Functional Organic Polymers

1st Iberian Symposium on Functional Organic Polymers

Synthesis of an Acidochromic and Nitroaromatic Responsive Hydrazone‐Linked Pillararene Framework by a Macrocycle‐To‐Framework Strategy

AbstractTailoring the properties of solid‐state organic luminescent materials using a bottom‐up design principle is highly desirable for many applications. Herein, we present a “macrocycle‐to‐framework” strategy to construct macrocycle‐functionalized and hydrazone‐linked functional organic polymers with bright yellowish‐green luminescence and unique solvatochromism behaviors by the condensation of a diacylhydrazine‐functionalized pillar[5]arene with tris(4‐formylbiphenyl)amine. Outperforming their non‐macrocycle‐incorporated counterparts, the pillar[5]arene‐containing materials display amplified sensitivity to acidic conditions with luminescent and colorimetric dual‐modal patterns assisted by the enhanced intramolecular charge transfer (ICT), and exhibit satisfactory responsiveness to nitrobenzene compounds through rapid luminescence quenching with high selectivity and a low detection limit, where the sensing process proceeds through multiple dynamic quenching pathways.

Synthesis of an Acidochromic and Nitroaromatic Responsive Hydrazone-Linked Pillararene Framework by a Macrocycle-To-Framework Strategy.

Tailoring the properties of solid-state organic luminescent materials using a bottom-up design principle is highly desirable for many applications. Herein, we present a "macrocycle-to-framework" strategy to construct macrocycle-functionalized and hydrazone-linked functional organic polymers with bright yellowish-green luminescence and unique solvatochromism behaviors by the condensation of a diacylhydrazine-functionalized pillar[5]arene with tris(4-formylbiphenyl)amine. Outperforming their non-macrocycle-incorporated counterparts, the pillar[5]arene-containing materials display amplified sensitivity to acidic conditions with luminescent and colorimetric dual-modal patterns assisted by the enhanced intramolecular charge transfer (ICT), and exhibit satisfactory responsiveness to nitrobenzene compounds through rapid luminescence quenching with high selectivity and a low detection limit, where the sensing process proceeds through multiple dynamic quenching pathways.

Magnetic Fluid Assisted Electro-Leaching for Metal Recovery

In current research, micro and nanoparticulate electrode materials have taken their place because they offer a large internal surface area with respect to the macroscopic dimensions of such electrodes [1]. The nano-impact method is a powerful tool that enables the characterization of individual particulate nano-objects in solution and study of their reactivity [2]. A three electrodes setup system working as a standard electrochemical cell is typically used. Magnetite (Fe3O4) nanoparticles with the strongest saturation magnetization of all naturally occurring iron oxides, combined with properties such as low toxicity, good biocompatibility, high stability, and low production costs, have attracted a lot of interest [3]. There is also substantial interest in their use as magnetic fluids, in data storage, in catalysis, and as electrode materials.In this work, magnetite micro and nanoparticles have been synthetized by chemical precipitation method in presence of surfactants or functional organic polymer. The effects of various parameters such as contact time, dosage of magnetite nanoparticles and the amount of functional groups on the adsorption capacity and efficiency of the treatment in the adsorption of copper and lithium are investigated. The use of surfactants to stabilize these synthesized nanoparticles is crucial, as Fe3O4 nanoparticles have high surface energies and tend to aggregate. Magnetic fluids constituted by dispersed functionalized magnetite particles are used as particulate electrode in different fluids and characterized into a three electrodes cell in order to evaluate their electrochemical behavior. A deeper understanding of the particulate electrode has been performed in situ on supported particles through electrochemical AFM/STM measurements, highlighting the behavior of the single aggregate. Together with the charge transfer characterization as a function of particles size and concentration, functionalization and fluid composition, practical applications of the particulate electrodes will be presented. Specifically, the use of particulate electrodes in the electrochemical metal recovery, showing the ions adsorption properties of magnetite particles as a function of surface functionalization and their electrochemical reduction at the magnetic fluid/current collector interphase will be discussed for specific systems, e.g. copper and lithium.1. V. Noack, H. Weller, A. Eychmu1ller, J. Phys. Chem. B, 106 (2002) 8514-85232. S.V Sokolov et al., Phys.Chem.Chem.Phys., 19 (2017) 283. K. Murugappan, ChemElectroChem, 1 (2014) 1211 – 1218

Direct and selective access to amino-poly(phenylene vinylenes)s with switchable properties by dimerizing polymerization of aminoaryl carbenes

Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. In this work, we exploit the capability of purposely designed mono- and bis-acyclic amino(aryl)carbenes to selectively dimerize as a general strategy to access diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s (N-PPV’s). The unique selectivity of the dimerization of singlet amino(aryl)carbenes, relative to putative C-H insertion pathways, is rationalized by DFT calculations. Of particular interest, unlike classical PPV’s, the presence of amino groups in α-position of C=C double bonds in N-PPV’s allows their physico-chemical properties to be manipulated in different ways by a simple protonation reaction. Hence, depending on the nature of the amino group (iPr2N vs. piperidine), either a complete loss of conjugation or a blue-shift of the maximum of absorption is observed, as a result of the protonation at different sites (nitrogen vs. carbon). Overall, this study highlights that singlet bis-amino(aryl)carbenes hold great promise to access functional polymeric materials with switchable properties, through a proper selection of their substitution pattern.

Polymer-Inorganic Thermoelectric Nanomaterials: Electrical Properties, Interfacial Chemistry Engineering, and Devices.

Though solar cells are one of the promising technologies to address the energy crisis, this technology is still far from commercialization. Thermoelectric materials offer a novel opportunity to convert energy between thermal and electrical aspects, which show the feasibility to improve the performance of solar cells via heat management and light harvesting. Polymer–inorganic thermoelectric nanocomposites consisting of inorganic nanomaterials and functional organic polymers represent one kind of advanced hybrid nanomaterials with tunable optical and electrical characteristics and fascinating interfacial and surface chemistry. During the past decades, they have attracted extensive research interest due to their diverse composition, easy synthesis, and large surface area. Such advanced nanomaterials not only inherit low thermal conductivity from polymers and high Seebeck coefficient, and high electrical conductivity from inorganic materials, but also benefit from the additional interface between each component. In this review, we provide an overview of interfacial chemistry engineering and electrical feature of various polymer–inorganic thermoelectric hybrid nanomaterials, including synthetic methods, properties, and applications in thermoelectric devices. In addition, the prospect and challenges of polymer–inorganic nanocomposites are discussed in the field of thermoelectric energy.

Reassessing the Physicochemical Properties of Ordered Mesoporous Polymer and Copolymer Nanocasts

AbstractNanocasting is a convenient way for preparing highly porous, nanostructured soft materials. Mesoporous polymer nanocasts have been reported for over a decade, however, several aspects remain to be explored further. To do so, we report a comprehensive investigation of the physicochemical characteristics of high surface area functional organic polymers and copolymers obtained by nanocasting. Divinylbenzene, styrene and chloromethyl styrene were selectively polymerized within the pores of mesoporous SBA‐15 or KIT‐6 silicas. Following template removal, the resulting materials were characterized. The nanocast mesoporous polymers were also modified to introduce functional groups. The success of the functionalization was assessed analytically and by model catalytic tests. The study points to the advantages of the hard templating method for structuring organic materials but also its limitations.

Synergistically Converting Carbon Dioxide into Cyclic Carbonates by Metalloporphyrin‐Based Cationic Polymers with Imidazolium Functionality

AbstractConsidering to the synergistic activation behavior in the cycloaddition reaction of CO2 to epoxides, the integration of metalloporphyrins and nucleophilic halide anions to afford functional organic polymers is one of the most important approaches and still remains challenging. Herein, a class of novel porphyrin‐based cationic polymer (Por‐CP) has been successfully prepared through a one‐pot and atom‐efficient polycondensation of pyrrole and tailorable imidazolium‐based ionic liquid bearing trialdehyde groups in refluxed propanoic acid. Subsequently, a direct metalation of Por‐CP with zinc acetate resulted in the formation of a zinc porphyrin‐based cationic polymer (ZnPor‐CP). The rigid and charged ZnPor‐CP having spatially‐separated active Zn‐porphyrin sites and abundant imidazolium functionalities in the covalently‐linked skeletons can cooperatively promote the reaction under mild conditions, thereby achieving an efficient unification of high activity and good recyclability.

Magnetic Fluids Assisted Electro-Leaching of Metals

In current research, micro and nanoparticulate electrode materials have taken their place because they offer a large internal surface area with respect to the macroscopic dimensions of such electrodes [1]. The nano-impact method is a powerful tool that enables the characterization of individual particulate nano-objects in solution and study of their reactivity [2]. A three electrodes setup system working as a standard electrochemical cell is typically used. Magnetite (Fe3O4) nanoparticles with the strongest saturation magnetization of all naturally occurring iron oxides, combined with properties such as low toxicity, good biocompatibility, high stability, and low production costs, have attracted a lot of interest [3]. There is also substantial interest in their use as magnetic fluids, in data storage, in catalysis, and as electrode materials.In this work, magnetite micro and nanoparticles have been synthetized by chemical precipitation method in presence of surfactants or functional organic polymer. The use of surfactants to stabilize these synthesized nanoparticles is crucial, as Fe3O4 nanoparticles have high surface energies and tend to aggregate. Magnetic fluids constituted by dispersed functionalized magnetite particles are used as particulate electrode in different fluids and characterized into a three electrodes cell in order to evaluate their electrochemical behavior. A deeper understanding of the particulate electrode has been performed in situ on supported particles through electrochemical AFM/STM measurements, highlighting the behavior of the single aggregate. Together with the charge transfer characterization as a function of particles size and concentration, functionalization and fluid composition, practical applications of the particulate electrodes will be presented. Specifically, the use of particulate electrodes in the electrochemical metal recovery, showing the ions adsorption properties of magnetite particles as a function of surface functionalization and their electrochemical reduction at the magnetic fluid/current collector interphase will be discussed for specific systems, e.g. copper and lithium.1.V. Noack, H. Weller, A. Eychmu1ller, J. Phys. Chem. B, 106 (2002) 8514-85232. S.V Sokolov et al., Phys.Chem.Chem.Phys., 19 (2017) 283. K. Murugappan, ChemElectroChem, 1 (2014) 1211 – 1218

Polyphenylene as an Active Support for Ru-Catalyzed Hydrogenolysis of 5-Hydroxymethylfurfural.

Selective transformation of biomass feedstocks to platform molecules is a key pursuit for sustainable chemical production. Compared to petrochemical processes, biomass transformation requires the defunctionalization of highly polar molecules at relatively low temperatures. As a result, catalysts based on functional organic polymers may play a prominent role. Targeting the hydrogenolysis of the platform chemical 5-hydroxymethylfurfural (5-HMF), here, we design a polyphenylene (PPhen) framework with purely sp2-hybridized carbons that can isolate 5-HMF via π-π stacking, preventing hemiacetal and humin formation. With good swellability, the PPhen framework here has successfully supported and dispersed seven types of metal particles via a newly developed swelling-impregnation method, including Ru, Pt, Au, Fe, Co, Ni, and Cu. Ru/PPhen is studied for 5-HMF hydrogenolysis, achieving a 92% yield of 2,5-dimethylfuran (DMF) under mild conditions, outperforming the state-of-the-art catalysts reported in the literature. In addition, PPhen helps perform a solventless reaction, achieving direct 5-HMF to DMF conversion in the absence of any liquid solvent or reagent. This approach in designing support-reactant/solvent/metal interactions will play an important role in surface catalysis.

Multiscale engineering of functional organic polymer interfaces for neuronal stimulation and recording

This review summarizes recent progress on chemistry and engineering techniques of organic polymers across a range of electrically insulating polymers, semiconducting polymers and conducting polymers for neural interfacing, stimulation and recording.

Electrochemistry of Particulate Electrodes Based on Magnetite Aggregates

In current research, micro and nanoparticulate electrode materials have taken their place because they offer a large internal surface area with respect to the macroscopic dimensions of such electrodes [1]. The nano-impact method is a powerful tool that enables the characterization of individual particulate nano-objects in solution and study of their reactivity [2]. A three electrodes setup system working as a standard electrochemical cell is typically used. Magnetite (Fe3O4) nanoparticles with the strongest saturation magnetization of all naturally occurring iron oxides, combined with properties such as low toxicity, good biocompatibility, high stability, and low production costs, have attracted a lot of interest [3]. There is also substantial interest in their use as magnetic fluids, in data storage, in catalysis, and as electrode materials. In this work, magnetite micro and nanoparticles have been synthetized by chemical precipitation method in presence of surfactants or functional organic polymer. The use of surfactants to stabilize these synthesized nanoparticles is crucial, as Fe3O4 nanoparticles have high surface energies and tend to aggregate. They also have high chemical activity. Magnetite particles are used as particulate electrode in different fluid and characterized into a three electrodes cell in order to evaluate their electrochemical behavior. A deeper understanding of the particulate electrode has been performed in situ on supported particles through electrochemical AFM/STM measurements, highlighting the behavior of the single aggregate. Together with the charge transfer characterization as a function of particles size and concentration, functionalization and fluid composition, practical applications of the particulate electrodes will be presented. Specifically, the use of particulate electrodes in the production of electrochemical sensors for glucose detection will be discussed. References Noack, H. Weller, A. Eychmu1ller, J. Phys. Chem. B, 106 (2002) 8514-8523V Sokolov et al., Phys.Chem.Chem.Phys., 19 (2017) 28Murugappan, ChemElectroChem, 1 (2014) 1211 – 1218

Combining 2D inorganic semiconductors and organic polymers at the frontier of the hard–soft materials interface

Recent advances in combining functional organic polymers with inorganic 2D semiconductors for nanoscale electronics are highlighted.

Direct Patterning of Organic Functional Polymers through Conventional Photolithography and Noninvasive Cross-Link Agents.

A new technique for direct patterning of functional organic polymers using commercial photolithography setups with a minimal loss of the materials' performances is reported. This result is achieved through novel cross-link agents made by boron- and fluorine-containing heterocycles that can react between themselves upon UV- and white-light exposure.

Decoration of heparin and bovine serum albumin on polysulfone membrane assisted via polydopamine strategy for hemodialysis

Renal failure brings about abnormality of waste and toxins and deposition in the body. In clinic, the waste and toxins in vitro are eliminated by hemodialysis device with polysulfone (PSF) porous membranes. In the work, decoration of heparin (Hep) and bovine serum albumin (BSA) on PSF membranes would be beneficial to improve the hemocompatibility and reduce the anaphylatoxin formation during hemodialysis. The PSF porous membranes are surface-modified by simply dipping them into dopamine aqueous solution for 8 h. Then, Hep and BSA are immobilized covalently onto the resultant membrane. Attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR) confirms that Hep and BSA are successfully introduced onto the surface of PSF membranes. Scanning electronic microscopy (SEM) and atomic force microscopy (AFM) display the changes of surface morphologies after modification. The result of water contact angle measurement shows that the hydrophilicity of PSF membranes is remarkably improved after coating polydopamine (pDA) and binding Hep and BSA. The experiments of hemocompatibility indicate that Hep and BSA grafted onto membranes suppress the adhesion of platelet and enhance the anticoagulation ability of PSF membranes. Furthermore, the protein adsorption tests reveal that Hep and BSA immobilized onto membranes depress the protein absorption and develop antifouling-protein ability of pristine membrane. This study proves a convenient and simple approach to graft two functional organic polymers which, respectively, play a vital role and then improve the hemocompatibility and biocompatibility of PSF membranes for their biomedical and blood-contacting applications.

Fine Pattern Transfer of Functional Organic Polymers by Nanoimprint

Nano structures on organic solar material are expected to improve power generation efficiency instead of bulk hetero junctions. In this study, we fabricated high aspect ratio nano structures using poly-3-hexylthiophene (P3HT) by a novel nano-imprint process. Fine structures 70-nm wide and 550-nm high were successful obtained. However, the pattern defects in the de-molding process were increased by basing on the increment of the pattern′s aspect ratio. We also investigated the relation between aspect ratio and defect yield.

Hypothetical physicochemical mechanisms of some intracellular processes: The hydrate hypothesis of mitosis and DNA replication

A DNA replication, mitosis, and binary fission hydrate hypothesis (MRH hypothesis) allowing non-trivial explanations for the physicochemical mechanisms of some intracellular processes is proposed. The hypothesis has a thermodynamic basis and is initiated by original experimental calorimetric and kinetic studies of the behavior of functional organic polymer and monomer substances in highly concentrated aqueous solutions. Experimental data demonstrating the occurrence of a short-range ordering in concentrated aqueous solutions of such substances are included. Hypothetical simple non-enzymatic unified mechanisms for the natural processes of DNA local unwinding preceding the start of duplication, DNA replication, formation and disappearance of the protein bonds between sister chromatids in the centromere region of eukaryotic DNA and in the centromere-like region of prokaryotic DNA, moving of daughter chromosomes apart to the opposite sides of cells in late anaphase, and formation of the nuclear envelopes in telophase and intracellular membranes between the newly formed nuclei in cytokinesis are formulated. The nature of a number of other intracellular phenomena is discussed.

Catalysis by metal nanoparticles supported on functional organic polymers

The preparation and catalytic applications of dispersed metal catalysts supported on organic functional polymers are presented. The advantages of these catalysts, such as the easy tailoring with respect to the nature of the used support, the “nanoscale” size control of metal crystallites by the polymer framework, the high accessibility and consequent catalytic activity in a proper liquid or liquid–vapor reaction systems are stressed. Various proposed catalytic processes making use of these materials are presented and evaluated, including multifunctional catalysis, e.g. redox-acid. Interesting peculiar aspects such as the enhancement of the hydrogenation rate by nitrogen containing moieties anchored to the polymer backbone are emphasised. When suitable, a comparison with catalysts based on inorganic supports is given.

Phase Separation of Carbon Nanotubes and Turbostratic Graphite Using a Functional Organic Polymer

Phase Separation of Carbon Nanotubes and Turbostratic Graphite Using a Functional Organic Polymer