Generic method for the detection of short & long chain PFAS extended to the lowest concentration levels of SERS capability.

The detection of the highly toxic per- and polyfluoroalkyl substances, PFAS, constitutes a challenging task in terms of developing a generic method that could be rapid and applicable simultaneously to both long and short-chain PFAS at ppt concentration level. In the present study, the method introduced by the USA Environmental Protection Agency, EPA, to detect surfactants, using methylene blue, MB, which is identified an ideal candidate for PFAS-MB ion pairing, is extended at the lowest concentration range by a simple additional step that involves the dissociation of the ion pairs in water. In this work, Surface Enhanced Raman Scattering, SERS, is applied via Ag nanocolloidal suspensions to probe MB and indirectly either/or both short-chain (perfluorobutyric acid, PFBA) and long-chain (perfluoloctanoic acid, PFOA) PFAS downt to 5 ppt. This method, which can be further optimized to sub-ppt level via a custom-made SERS-PFAS dedicated Raman system, offers the possibility to be applied to either specific PFAS (both short and long-chain) in a targeted analysis or to total PFAS in a non-targeted analysis at very low detection limits, following any type of MB detection method in aqueous solutions and obviously with any type of SERS substrate.

Raman Spectroscopy Unfolds the Fate and Transformation of SWCNTs after Abrasive Wear of Epoxy Floor Coatings.

Nanomaterials are integrated within consumer products to enhance specific properties of interest. Their release throughout the lifecycle of nano-enabled products raises concerns; specifically, mechanical strains can lead to the generation of fragmented materials containing nanomaterials. We investigated the potential release of single-walled carbon nanotubes (SWCNTs-brand TUBALL™) from epoxy composite materials. A pin-on-disk-type tribometer was used for the accelerated mechanical aging of the nanocomposites. A pristine nanocomposite material, abraded material and debris obtained from the abrasion in the tribometer were analyzed by Raman spectroscopy. The airborne-produced particles were captured using particle collectors. Stat Peel's Identifier C2 system was used to monitor the SWCNT content of respirable particles produced during the abrasion test. The SWCNT amounts found were below the LoQ. The Raman spectra conducted on the Stat Peel filters helped identify the presence of free SWCNTs released from the epoxy matrix, although they were notably scarce. Raman spectroscopy has been proved to be a crucial technique for the identification, characterization and assessment of structural changes and degradation in SWCNTs that occurred during the abrasion experiments.

Improvement of Water Vapor Permeability in Polypropylene Composite Films by the Synergy of Carbon Nanotubes and ß-Nucleating Agents.

A notable application of polymeric nanocomposites is the design of water vapor permeable (WVP) membranes. "Breathable" membranes can be created by the incorporation of micro/nanofillers, such as CaCO3, that interrupt the continuity of the polymeric phase and when subjected to additional uniaxial or biaxial stretching this process leads to the formation of micro/nanoporous structures. Among the candidate nanofillers, carbon nanotubes (CNTs) have demonstrated excellent intrinsic WVP properties. In this study, chemically modified MWCNTs with oligo olefin-type groups (MWCNT-g-PP) are incorporated by melt processes into a PP matrix; a ß-nucleating agent (ß-ΝA) is also added. The crystallization behavior of the nanocomposite films is evaluated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The WVP performance of the films is assessed via the "wet" cup method. The nanohybrid systems, incorporating both MWCNT-g-PP and ß-NA, exhibit enhanced WVP compared to films containing only MWCNT-g-PP or ß-NA. This improvement can be attributed to the significant increase in the growth of α-type crystals taking place at the edges of the CNTs. This increased crystal growth exerts a form of stress on the metastable ß-phase, thereby expanding the initial microporosity. In parallel, the coexistence of the inherently water vapor-permeable CNTs, further enhances the water vapor permeability reaching a specific water vapor transmission rate (Sp.WVTR) of 5500 µm.g/m2.day in the hybrid composite compared to 1000 µm.g/m2.day in neat PP. Notably, the functionalized MWCNT-g-PP used as nanofiller in the preparation of the "breathable" PP films demonstrated no noteworthy cytotoxicity levels within the low concentration range used, an important factor in terms of sustainability.

Production efficiency and properties of poly(3hydroxybutyrate-co-3hydroxyvalerate) generated via a robust bacterial consortium dominated by Zoogloea sp. using acidified discarded fruit juices as carbon source.

In the current study, a mixed microbial culture (MMC) of polyhydroxyalkanoates (PHAs) producers was developed under nutrient stress and was assessed as biocatalyst for the production of high-yielding PHAs from fermented (acidified) discarded fruit juices (DFJ). The structure of the MMC was analyzed periodically to determine its microbial dynamics, revealing that Zoogloae sp. dominated throughout the operation of the system. The efficiency of PHAs production from the MMC was further optimized in batch mode by altering the ratio of C to N, the ratio of carbon sources (propionate and butyrate), and the initial pH, and subsequently different fermentation mixtures of acidified DFJ were assessed as substrates at optimal conditions. Upon solvent extraction, the properties of recovered PHAs were analyzed, showing that in all cases P(3HB-co-3HV) was produced, with Tm ranging from 90.5 to 168.8 °C, and maximum obtained yields 54.61 ± 4.31 % and 43.27 ± 2.13 %, from synthetic substrates and DFJ, respectively. Overall, it was shown that the developed MMC can be efficiently applied as biocatalyst for the exploitation of sugary wastewaters, such as DFJ, towards bio-based and biodegradable plastics bearing the required properties to substitute fossil plastics, into the concept of a circular economy.

High Catalytic Efficiency of a Nanosized Copper-Based Catalyst for Automotives: A Physicochemical Characterization.

The global trend in restrictions on pollutant emissions requires the use of catalytic converters in the automotive industry. Noble metals belonging to the platinum group metals (PGMs, platinum, palladium, and rhodium) are currently used for autocatalysts. However, recent efforts focus on the development of new catalytic converters that combine high activity and reduced cost, attracting the interest of the automotive industry. Among them, the partial substitution of PGMs by abundant non-PGMs (transition metals such as copper) seems to be a promising alternative. The PROMETHEUS catalyst (PROM100) is a polymetallic nanosized copper-based catalyst for automotives prepared by a wet impregnation method, using as a carrier an inorganic mixed oxide (CeO2-ZrO2) exhibiting elevated oxygen storage capacity. On the other hand, catalyst deactivation or ageing is defined as the process in which the structure and state of the catalyst change, leading to the loss of the catalyst's active sites with a subsequent decrease in the catalyst's performance, significantly affecting the emissions of the catalyst. The main scope of this research is to investigate in detail the effect of ageing on this low-cost, effective catalyst. To that end, a detailed characterization has been performed with a train of methods, such as SEM, Raman, XRD, XRF, BET and XPS, to both ceria-zirconia mixed inorganic oxide support (CZ-fresh and -aged) and to the copper-based catalyst (PROM100-fresh and -aged), revealing the impact of ageing on catalytic efficiency. It was found that ageing affects the Ce-Zr mixed oxide structure by initiating the formation of distinct ZrO2 and CeO2 structures monitored by Raman and XRD. In addition, it crucially affects the morphology of the sample by reducing the surface area by a factor of nearly two orders of magnitude and increasing particle size as indicated by BET and SEM due to sintering. Finally, the Pd concentration was found to be considerably reduced from the material's surface as suggested by XPS data. The above-mentioned alterations observed after ageing increased the light-off temperatures by more than 175 °C, compared to the fresh sample, without affecting the overall efficiency of the catalyst for CO and CH4 oxidation reactions. Metal particle and CeZr carrier sintering, washcoat loss as well as partial metal encapsulation by Cu and/or CeZrO4 are identified as the main causes for the deactivation after hydrothermal ageing.

Environmentally Friendly Hybrid Organic-Inorganic Halogen-Free Coatings for Wood Fire-Retardant Applications.

Wood and wood-based products are extensively used in the building sector due to their interesting combination of properties. Fire safety and fire spread, however, are of utmost concern for the protection of buildings. Therefore, in timber structures, wood must be treated with fire-retardant materials in order to improve its reaction to fire. This article highlights the flame retardancy of novel hybrid organic-inorganic halogen-free coatings applied on plywood substrates. For this purpose, either a huntite-rich mineral (H5) or its modified nano-Mg (OH)2 type form (H5-m), acting as an inorganic (nano) filler, was functionalized with reactive oligomers (ROs) and incorporated into a waterborne polymeric matrix. A water-soluble polymer (P (SSNa-co-GMAx)), combining its hydrophilic nature with functional epoxide groups, was used as the reactive oligomer in order to enhance the compatibility between the filler and the matrix. Among various coating compositions, the system composed of 13% polymeric matrix, 73% H5 and 14% ROs, which provided the best coating quality and flame retardancy, was selected for the coating of plywood on a larger scale in one or two layers. The results indicated that the novel plywood coating systems with the addition of ecological coating formulations (WF-13, WF-14 and WF-15), prepared at two layers, reached Euroclass B according to EN13501-1, which is the best possible for fire systems applied to wood.

Glycidyl Methacrylate-Based Copolymers as Healing Agents of Waterborne Polyurethanes.

Self-healing materials and self-healing mechanisms are two topics that have attracted huge scientific interest in recent decades. Macromolecular chemistry can provide appropriately tailored functional polymers with desired healing properties. Herein, we report the incorporation of glycidyl methacrylate-based (GMA) copolymers in waterborne polyurethanes (WPUs) and the study of their potential healing ability. Two types of copolymers were synthesized, namely the hydrophobic P(BA-co-GMAy) copolymers of GMA with n-butyl acrylate (BA) and the amphiphilic copolymers P(PEGMA-co-GMAy) of GMA with a poly(ethylene glycol) methyl ether methacrylate (PEGMA) macromonomer. We demonstrate that the blending of these types of copolymers with two WPUs leads to homogenous composites. While the addition of P(BA-co-GMAy) in the WPUs leads to amorphous materials, the addition of P(PEGMA-co-GMAy) copolymers leads to hybrid composite systems varying from amorphous to semi-crystalline, depending on copolymer or blend composition. The healing efficiency of these copolymers was explored upon application of two external triggers (addition of water or heating). Promising healing results were exhibited by the final composites when water was used as a healing trigger.

Flame Retardant Nano-Structured Fillers from Huntite/Hydromagnesite Minerals.

In the current study, we propose a simple hydrothermal pathway to synthesize nano-structured Mg(OH)2 after application of thermal decomposition followed by hydration of commercial minerals based on hydromagnesite and huntite. The synthesis of nano-materials is performed without the use of any catalyst. The effect of decomposition temperature on the hydrothermal synthesis of Mg(OH)2 is extensively studied. It is shown that the morphology of resulting structures consists typically of particles ~200 nm in diameter and ~10 nm in thickness. Study of the structure at the molecular level designates the composition and supports the nano-sized characteristics of the produced materials. The associated thermal properties combined with the corresponding optical properties suggest that the material may be used as a flame retardant filler with enhanced transparency. In this concept, the flame retardancy of composite coatings containing the produced nano-sized Mg(OH)2 was examined in terms of limiting oxygen index (LOI), i.e., the minimum concentration of oxygen that just supports flaming combustion.

Wet-chemistry assembly of one-dimensional nanowires: switching characteristics of a known spin-crossover iron(II) complex through Raman spectroscopy.

In this study, a simple, fast, one-pot approach for the isolation of nanowires (NWs) in coordination chemistry is reported. Nanowires (NWs) of spin-crossover (SCO) materials are extremely rare. Here, an innovative and easy synthetic process was developed to prepare NWs of a switchable polymorph of the known complex trans-[Fe(NCS)2(abpt)2] using a wet-chemistry approach for the first time; abpt is the bidentate chelating ligand 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole. The remarkable smoothness of the high-spin to low-spin transition, monitored through variable-temperature (300-80 K) Raman microscopy, compared with the sharp transition exhibited by the polycrystalline material, demonstrates the effect of the topological properties on the physical phenomena of the system.

Collagen orientation probed by polarized Raman spectra can serve as differential diagnosis indicator between different grades of meniscus degeneration.

The purpose of the present study was to analyze normal and degenerated menisci with Raman methodology on thin sections of formalin fixed paraffin embedding tissues and to correlate the Raman findings with the grade of meniscus degeneration. Menisci (n = 27) were removed from human knee joints after total knee replacement or meniscectomy. Following routine histopathological analysis to determine the grade of meniscal lesions obtained from healthy and degenerated formaline fixed paraffin embedded (FFPE) meniscal sections, Raman polarization approach was applied to evaluate the orientation of collagen fibrils in different levels of the same 5 µm thick FFPE meniscal tissue sections, used for histopathological assessment. We collected Raman spectra in two different polarization geometries, v-HH and v-VV, and calculated the mean value of the v-HH/v-VV intensity ratio of two Raman bands, sensitive and non-sensitive to the molecular orientation. The collagen specific amide I band at 1665 cm-1, has the higher sensitivity dependence on the Raman polarization. The mean values of ratio v-HH/v-VV of the 1665 cm-1 peak intensity was significantly higher in healthy, mean ± SD: 2.56 ± 0.46, compared to degenerated menisci, mean ± SD: 1.85 ± 0.42 (p = 0.0014). The mean values of v-HH/v-VV intensity ratio were 2.18 and 1.50 for low and high degenerated menisci, respectively (p < 0.0001). The difference of peak intensities in the two laser polarizations is decreased in the degenerated meniscus; this difference is diminishing as the degeneration increases. The v-HH/v-VV ratio was also of significant difference in low as compared to control and high grade meniscus lesions (p = 0.036 and p < 0.0001, respectively) offering valuable information for the approach of its biology and function. In the present study we showed that the 5 µm thick sections can be used for Raman analysis of meniscal tissue with great reliability, in terms of sensitivity, specificity, false-negative and false-positive results. Our data introduce the interesting hypothesis that compact portable Raman microscopy on tissue sections can be used intra-operatively for fast diagnosis and hence, accurate procedure design in the operating room.

Patterned, organoid-based cartilaginous implants exhibit zone specific functionality forming osteochondral-like tissues in vivo.

Tissue engineered constructs have the potential to respond to the unmet medical need of treating deep osteochondral defects. However, current tissue engineering strategies struggle in the attempt to create patterned constructs with biologically distinct functionality. In this work, a developmentally-inspired modular approach is proposed, whereby distinct cartilaginous organoids are used as living building blocks. First, a hierarchical construct was created, composed of three layers of cartilaginous tissue intermediates derived from human periosteum-derived cells: (i) early (SOX9), (ii) mature (COL2) and (iii) (pre)hypertrophic (IHH, COLX) phenotype. Subcutaneous implantation in nude mice generated a hybrid tissue containing one mineralized and one non-mineralized part. However, the non-mineralized part was represented by a collagen type I positive fibrocartilage-like tissue. To engineer a more stable articular cartilage part, iPSC-derived cartilage microtissues (SOX9, COL2; IHH neg) were generated. Subcutaneous implantation of assembled iPSC-derived cartilage microtissues resulted in a homogenous cartilaginous tissue positive for collagen type II but negative for osteocalcin. Finally, iPSC-derived cartilage microtissues in combination with the pre-hypertrophic cartilage organoids (IHH, COLX) could form dual tissues consisting of i) a cartilaginous safranin O positive and ii) a bony osteocalcin positive region upon subcutaneous implantation, corresponding to the pre-engineered zonal pattern. The assembly of functional building blocks, as presented in this work, opens possibilities for the production of complex tissue engineered implants by embedding zone-specific functionality through the use of pre-programmed living building blocks.

Fe(II) Spin Crossover/Polymer Hybrid Materials: Investigation of the SCO Behavior via Temperature-Dependent Raman Spectroscopy, Physicochemical Characterization and Migration Release Study.

Polymeric composites constitute an appealing class of materials with applications in various fields. Spin crossover (SCO) coordination complexes are switchable materials with potential use in data storage and sensors. Their incorporation into polymers can be considered an effective method for their wider practical application. In this study, Fe(II) SCO/polylactic acid hybrid polymeric composites have been prepared by film casting. The mononuclear coordination complex [Fe{N(CN)2}2(abpt)2] was incorporated into polylactic acid. The morphological, structural and thermoanalytical characterization of the composite films were performed via scanning electron microscopy (SEM), attenuated total reflectance (ATR/FTIR), Raman spectroscopy and differential scanning calorimetry (DSC). In addition, the migration release study (MRS) of the SCO compound from the polymeric matrix into the food simulant 50% v/v water/ethanol solution was also examined via UV/Vis absorption. Of particular interest was the investigation of the SCO behavior of the coordination complex after its incorporation into the polymer matrix; it was accomplished by temperature-dependent micro-Raman spectroscopy. The described attempt could be considered a preparatory step toward the development of SCO-based temperature sensors integrated into food packaging materials.

Poly(ethylene Terephthalate) Carbon-Based Nanocomposites: A Crystallization and Molecular Orientation Study.

Hybrid polymeric materials incorporating carbon nanostructures or inorganic constituents stand as a promising class of materials exhibiting distinct but also complementary features. Carbon nanotubes have been proposed as unique candidates for polymer reinforcement; however, sustained efforts are further needed in order to make full use of their potential. The final properties of the reinforced polymer are controlled in part by the morphology and the eventual molecular orientation of the polymer matrix. In the present study, multiwall carbon nanotubes (MWCNTs) were utilized in order to reinforce polyethylene terephthalate (PET) composites. The effect of CNTs on the crystallization and the orientation of the structurally hybridized polymeric material has been investigated from the perspective of assessing their impact on the final properties of a relevant nanocomposite product. Functionalized MWCNTs were used to achieve their optimal dispersion in the polymer matrix. The physical properties of the composites (i.e., crystallinity and orientation) were characterized via differential scanning calorimetry, X-ray diffraction, and polarized Raman microscopy. The addition of well-dispersed CNTs acted as a nucleation agent, increasing the crystallization of the polyethylene terephthalate matrix and differentiating the orientation of both CNTs and macromolecular chains.

Surface characterization of monolithic zirconia submitted to different surface treatments applying optical interferometry and raman spectrometry.

This study evaluated roughness parameters and phase transformation of monolithic zirconia ceramics after various mechanical and laser thermal treatments. Fully sintered monolithic zirconia cylinder specimens were divided to five groups, according to the applied surface treatment: CL: control, GB: grit-blasted with glass particles. AL50: grit-blasted with 50 µm alumina particles, AL90: grit-blasted with 90 µm dyed-alumina particles and FEML: subjected to femto laser thermal treatment. Six roughness parameters (Sa, Sq, Sz, Sci, Svi and Sdr) were measured by optical profilometry. Phase transformation in zirconia was determined by micro-Raman spectroscopy. The highest roughness values were recorded in AL90 and FEML groups, followed by AL50. AL90 presented statistically higher monoclinic phase content compared to all other groups. Control and GB groups presented similar roughness without phase transformation. Laser thermal treatment causes minimal destruction of the zirconia surface, and can be suggested as an alternative to other roughening treratments, for enhancing the adhesive potential to dentin.

Modeling the Solvent Extraction of Cadmium(II) from Aqueous Chloride Solutions by 2-pyridyl Ketoximes: A Coordination Chemistry Approach.

The goal of this work is to model the nature of the chemical species [CdCl2(extractant)2] that are formed during the solvent (or liquid-liquid) extraction of the toxic cadmium(II) from chloride-containing aqueous media using hydrophobic 2-pyridyl ketoximes as extractants. Our coordination chemistry approach involves the study of the reactions between cadmium(II) chloride dihydrate and phenyl 2-pyridyl ketoxime (phpaoH) in water-containing acetone. The reactions have provided access to complexes [CdCl2(phpaoH)2]∙H2O (1∙H2O) and {[CdCl2(phpaoH)]}n (2); the solid-state structures of which have been determined by single-crystal X-ray crystallography. In both complexes, phpaoH behaves as an N,N'-bidentate chelating ligand. The complexes have been characterized by solid-state IR and Raman spectra, and by solution 1H NMR spectra. The preparation and characterization of 1∙H2O provide strong evidence for the existence of the species [CdCl2(extractant)2] that have been proposed to be formed during the liquid-liquid extraction process of Cd(II), allowing the efficient transfer of the toxic metal ion from the aqueous phase into the organic phase.

A Known Iron(II) Complex in Different Nanosized Particles: Variable-Temperature Raman Study of Its Spin-Crossover Behavior.

The spin-crossover (SCO) polymorph B (complex 1) of the known compound [FeII{N(CN)2}2(abpt)2], where abpt is 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole, has been prepared in three different particle sizes averaging ∼300 (sample 1a), ∼80 (sample 1b), and ∼20 nm (sample 1c). Two independent octahedral molecules possessing Fe1 and Fe2 were found to be present in the crystal of B. Magnetostructural relationships had established that at room temperature both FeII sites are in the high-spin state (HS-HS), whereas a decrease in the temperature to 90 K induces the complete high-spin to low-spin conversion of the Fe1 site, with Fe2 remaining in the high-spin state (LS-HS). The three samples have been characterized by elemental analyses, ATR spectra, solution UV/vis spectra (to exclude resonance Raman effects) and powder X-ray diffraction patterns, while their morphological characteristics have been examined by scanning electron microscopy (SEM). The SCO behavior of the originally prepared sample 1a has been monitored in detail by variable-temperature Raman studies in the 300-80 K range using mainly low-frequency ν(Fe-N) and δ(NFeN) modes and the ν(C≡N) mode of the axial dicyanamido groups as spin-sensitive vibrations. The new peaks that appear in the low-temperature Raman spectra of the LS-HS form of the complex are reproduced in the calculated spectrum of the LS state of [FeII{N(CN)2}2(abpt)2]. The influence of the average particle size on the SCO properties of 1 has also been studied by variable-temperature Raman spectra. The studies indicate that, during the HS-HS → LS-HS transition, the latter form of the complex appears at higher temperatures for the smaller particles; the T1/2 shift accomplished by manipulating the particle size within a range of roughly 1 order of magnitude (300-20 nm) may be as high as ∼30 K. The SCO features of 1, as deduced from the Raman study, are in excellent agreement with those derived from a traditional variable-temperature magnetic susceptibility study, indicating the utility of the former.

Thermal dewetting tunes surface enhanced resonance Raman scattering (SERRS) performance.

Surface Enhanced Raman Spectroscopy (SERS) belongs to the techniques of ultra-sensitive chemical analysis and involves both identification and quantification of molecular species. Despite the fact that theoretically derived enhancement factors imply that even single molecules may be identified, which in some cases has indeed been experimentally observed, the application of this specific technique as an analytical tool is still an open field of research due to the need for reproducible, stable and simple to prepare SERS active substrates. The current work attempts to contribute to the already established knowledge on the substrates of metallic nanostructured films by a systematic study on the optimal conditions required for the detection of a specifically selected (model) material, the antitumor drug mitoxantrone (MTX). Au thin film deposition on Si substrates, by sputtering followed by solid state thermal dewetting is a facile and reproducible way to prepare Au nanoparticles with the desired particle size distribution. This offers control over their optical - plasmon resonance - properties that can be efficiently tailored to the prerequisites of the resonance Raman conditions, associated to the species under inspection, which is a supplement to the overall enhancement scattering factor. Furthermore, this work attempts to confirm the quantification capabilities of SERS, via the aforementioned substrates, in view of extending SERS applications to food safety, biosensors etc.

The Essential Elements of a Risk Governance Framework for Current and Future Nanotechnologies.

Societies worldwide are investing considerable resources into the safe development and use of nanomaterials. Although each of these protective efforts is crucial for governing the risks of nanomaterials, they are insufficient in isolation. What is missing is a more integrative governance approach that goes beyond legislation. Development of this approach must be evidence based and involve key stakeholders to ensure acceptance by end users. The challenge is to develop a framework that coordinates the variety of actors involved in nanotechnology and civil society to facilitate consideration of the complex issues that occur in this rapidly evolving research and development area. Here, we propose three sets of essential elements required to generate an effective risk governance framework for nanomaterials. (1) Advanced tools to facilitate risk-based decision making, including an assessment of the needs of users regarding risk assessment, mitigation, and transfer. (2) An integrated model of predicted human behavior and decision making concerning nanomaterial risks. (3) Legal and other (nano-specific and general) regulatory requirements to ensure compliance and to stimulate proactive approaches to safety. The implementation of such an approach should facilitate and motivate good practice for the various stakeholders to allow the safe and sustainable future development of nanotechnology.

Polymer Conformation under Confinement.

The conformation of polymer chains under confinement is investigated in intercalated polymer/layered silicate nanocomposites. Hydrophilic poly(ethylene oxide)/sodium montmorillonite, PEO/Na⁺-MMT, hybrids were prepared utilizing melt intercalation with compositions where the polymer chains are mostly within the ~1 nm galleries of the inorganic material. The polymer chains are completely amorphous in all compositions even at temperatures where the bulk polymer is highly crystalline. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) is utilized to investigate the conformation of the polymer chains over a broad range of temperatures from below to much higher than the bulk polymer melting temperature. A systematic increase of the gauche conformation relatively to the trans is found with decreasing polymer content both for the C⁻C and the C⁻O bonds that exist along the PEO backbone indicating that the severe confinement and the proximity to the inorganic surfaces results in a more disordered state of the polymer.

A unique copper(ii)-assisted transformation of acetylacetone dioxime in acetone that leads to one-dimensional, quinoxaline-bridged coordination polymers.

The reactions of copper(ii) carboxylate sources with acetylacetone dioxime (acacdoH2) in Me2CO have been studied and a novel, metal ion-assisted ligand transformation has been discovered. The reaction of [Cu2(diba)4(dibaH)2] and acacdoH2 (1 : 1.5) in Me2CO has provided access to the complex {[Cu2(diba)4(qunx)]}n (1) in low yield (25-30%), where dibaH is 3,3-dimethylbutyric acid and qunx is quinoxaline. The [Cu2(piv)4(pivH)2]/acacdoH2 (1 : 1.5) reaction system in warm Me2CO, where pivH is pivalic acid, gave the analogous complex {[Cu2(piv)4(qunx)]}n (2) in moderate yield (∼50%). Complexes 1 and 2 can be easily prepared by the direct 1 : 1 reactions between the corresponding copper(ii) carboxylate starting materials and qunx in Me2CO and MeOH, respectively. The formation of coordinated qunx in 1 and 2 is CuII-promoted (assisted) as suggested by the failure to synthesize the free qunx by a variety of reactions of acacdoH2 and Me2CO under aerobic conditions in the absence or even the presence of dibaH and pivH, respectively. The observed acacdoH2 → qunx transformation is catalytic and new in the chemistry of the dioximes of ß-diketones, and a mechanism has been proposed based on well-established reactions of organic chemistry. The mechanism is based on a double Beckmann rearrangement-type transformation and the overall scheme is represented by the 1 : 1 : 1 reaction between acacdoH2, Me2CO and O2. Complexes 1 and 2 have similar molecular structures consisting of paddle-wheel {Cu2(η1:η1:µ-O2CR)4} units bridged by qunx ligands in a zigzag 1D chain arrangement. The geometry of the CuII ions is square pyramidal with a quinoxaline nitrogen atom occupying the apical position at each metal ion. Weak H bonds are present within the chains, the donors being qunx carbon atoms and the acceptors being coordinated carboxylate oxygen atoms. Neighbouring chains interact through C-Hπ interactions between diba-/piv- methyl groups and the "pyrazine" part of qunx forming layers which are stacked along the b (1) or a (2) axis through weak van der Waals interactions. The packing of the layers is different in the two structures, due to the different nature of the carboxylate ligands. Hirshfeld surface analysis of the two structures reveals the similarity of the interchain (intralayer) interactions. The IR and Raman data of 1 and 2 are discussed in terms of the coordination mode of the carboxylate groups and permit assignments of some characteristic bands/peaks of coordinated qunx. Dc magnetic susceptibility studies in the 1.8-310 K range reveal very strong antiferromagnetic CuIICuII exchange interactions within the carboxylate-bridged Cu2 units (J = -479 K for 1 and -532 K for 2 using the H = - J∑S1·S2 spin Hamiltonian) and weaker antiferromagnetic interactions between the Cu2 units via the qunx superexchange pathways, with the latter being ∼10% in strength compared to the former. A critical discussion of the acacdoH2 → qunx transformation in 1 and 2 is provided in the light of other impressive, recently discovered CuII-assisted transformations of acacdoH2, pointing out the key role of the solvent in the processes known to date.