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This work focuses on the incorporation of 2D carbon nanomaterials, such as graphene oxide (GO), reduced graphene oxide (rGO) and graphene nanoplatelets (GNPs), into polypropylene (PP) via melt mixing. The addition of these 2D carbon nanostructured networks offers a novel approach to enhancing/controlling the water vapor permeable capabilities of PP composite membranes, widely used in industrial applications, such as technical (building roof membranes) or medical (surgical gowns) textiles. The study investigates how the dispersion and concentration of these graphene nanomaterials within the PP matrix influence the microstructure and water vapor permeability (WVP) performance. The WVP measurements were conducted via the "wet" cup method. The presence of either GO, rGO or GNPs in the new polyolefin composite membranes revealed 6- to 7-fold enhanced WVP values compared to pristine PP. This improvement is attributed to the nanoindentations created at the interface of the carbon nanoinclusions with the polymer matrix in the form of nanopores that facilitate water vapor diffusion. In the particular case of GO and rGO, residual oxidative groups might contribute to the WVP as well. This is the first study to compare GO, rGO and even GNP inclusions under identical conditions, providing deeper insights into the mechanisms driving the observed improvements in WVP performance.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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.

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 CaCO 3 , 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 β-nucleating agent (β-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 β-NA, exhibit enhanced WVP compared to films containing only MWCNT-g-PP or β-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 β-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/m 2 .day in the hybrid composite compared to 1000 μm.g/m 2 .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.

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 T m 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., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Gerasimos Lyberatos reports financial support was provided by General Secretariat for Research and Technology. Gerasimos Lyberatos reports a relationship with General Secretariat for Research and Technology that includes: funding grants., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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.

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 (CeO 2 -ZrO 2 ) 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 ZrO 2 and CeO 2 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 CH 4 oxidation reactions. Metal particle and CeZr carrier sintering, washcoat loss as well as partial metal encapsulation by Cu and/or CeZrO 4 are identified as the main causes for the deactivation after hydrothermal ageing., Competing Interests: The authors declare no conflict of interest.

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.

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.

The current work reports on a systematic study related to the vibrational modes of the ester carbonyl group in drawn polyesters. We have observed and try to explain how the presence of aromatic units in the molecular structure substantially affects the respective elements of the Raman tensor in contrast to the dipole moment derivative vector which is only marginally influenced. The work is based on the collection of polarized Raman spectra and FTIR dichroism measurements on the one hand and on DFT calculations on the other. The experimental data were obtained from uniaxially stretched aliphatic and semi-aromatic polyesters. The calculations were applied on relevant oriented oligomers and allowed the extraction: (i) of reliable Raman/FTIR vibrational spectra and (ii) the components of the dipole moment derivative and Raman tensor of the vibrational modes and in particular the ones involving the ester carbonyl group. Experimental data indicate that the intensity of the ester carbonyl band is considerably enhanced in the Raman spectra of semi-aromatic polyesters, which results from a considerable enhancement of the related coupling coefficient. Furthermore, the angles of the principle Raman tensor axis are rotated so that the element of the tensor with the greatest value is oriented towards the direction designated by the segment. The latter explains the peculiar experimentally indicated anisotropy, through the ester carbonyl stretching, for the case of semi-aromatic polyesters, which is totally different with that observed in the aliphatic ones., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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.

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., (© 2021. The Author(s).)

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., (Copyright © 2021. Published by Elsevier Ltd.)

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.

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.

The goal of this work is to model the nature of the chemical species [CdCl 2 (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 [CdCl 2 (phpaoH) 2 ]∙H 2 O ( 1 ∙H 2 O) and {[CdCl 2 (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 1 H NMR spectra. The preparation and characterization of 1 ∙H 2 O provide strong evidence for the existence of the species [CdCl 2 (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., Competing Interests: The authors declare no conflict of interest.

The spin-crossover (SCO) polymorph B (complex 1) of the known compound [Fe II {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 Fe II 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 [Fe II {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 T 1/2 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.

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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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.

The reactions of copper(ii) carboxylate sources with acetylacetone dioxime (acacdoH 2 ) in Me 2 CO have been studied and a novel, metal ion-assisted ligand transformation has been discovered. The reaction of [Cu 2 (diba) 4 (dibaH) 2 ] and acacdoH 2 (1 : 1.5) in Me 2 CO has provided access to the complex {[Cu 2 (diba) 4 (qunx)]} n (1) in low yield (25-30%), where dibaH is 3,3-dimethylbutyric acid and qunx is quinoxaline. The [Cu 2 (piv) 4 (pivH) 2 ]/acacdoH 2 (1 : 1.5) reaction system in warm Me 2 CO, where pivH is pivalic acid, gave the analogous complex {[Cu 2 (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 Me 2 CO and MeOH, respectively. The formation of coordinated qunx in 1 and 2 is Cu II -promoted (assisted) as suggested by the failure to synthesize the free qunx by a variety of reactions of acacdoH 2 and Me 2 CO under aerobic conditions in the absence or even the presence of dibaH and pivH, respectively. The observed acacdoH 2 → qunx transformation is catalytic and new in the chemistry of the dioximes of β-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 acacdoH 2 , Me 2 CO and O 2 . Complexes 1 and 2 have similar molecular structures consisting of paddle-wheel {Cu 2 (η 1 :η 1 :μ-O 2 CR) 4 } units bridged by qunx ligands in a zigzag 1D chain arrangement. The geometry of the Cu II 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 Cu II Cu II exchange interactions within the carboxylate-bridged Cu 2 units (J = -479 K for 1 and -532 K for 2 using the H = - J∑S 1 ·S 2 spin Hamiltonian) and weaker antiferromagnetic interactions between the Cu 2 units via the qunx superexchange pathways, with the latter being ∼10% in strength compared to the former. A critical discussion of the acacdoH 2 → qunx transformation in 1 and 2 is provided in the light of other impressive, recently discovered Cu II -assisted transformations of acacdoH 2 , pointing out the key role of the solvent in the processes known to date.

A novel concept for the use of an immiscible and non-meltable polymer, such as sodium polystyrene sulfonate (PSSNa), in order to prepare polyethylene non-woven breathable membranes is described. Membranes were fabricated by melt compounding of properly functionalized PE (P(E- co -AA)) and PSSNa (P(SSNa- co -GMA)) copolymers in the presence of water soluble polyethylene glycol (PEG). The inability of PSSNa derivatives to be melted was overcome by using PEG, which was easily meltable thus inducing PSSNa processability improvement. PEG was removed after membrane fabrication and therefore also acted as a porogen. Carbon nanotubes, functionalized with PSSNa moieties or alkyl groups, were also incorporated in the membranes with the aim of improving the porous connectivity and increasing the water vapor transmission rate. The morphology of the membranes was investigated through Scanning Electron Microscopy (SEM). Water vapor transmission rate (permeation) (WVTR) measurements for the porous membranes showed increased values in comparison with the neat PE ones. A further increase of WVTR was observed with the addition of CNTs to the polymer membranes.

Objectives: Dental zirconia restorations should present long-term clinical survival and be in service within the oral environment for many years. However, low temperature degradation could affect their mechanical properties and survival. The aim of this study was to investigate the effect of in vitro aging on the flexural strength of yttrium-stabilized (Y-TZP) zirconia ceramics for ceramic restorations., Methods: One hundred twenty bar-shaped specimens were prepared from two ceramics (ZENO Zr (WI) and IPS e.max(®) ZirCAD (IV)), and loaded until fracture according to ISO 6872. The specimens from each ceramic (nx=60) were divided in three groups (control, aged for 5h, aged for 10h). One-way ANOVA was used to assess statistically significant differences among flexural strength values (P<0.05). The variability of the flexural strength values was analyzed using the two-parameter Weibull distribution function, which was applied for the estimation of Weibull modulus (m) and characteristic strength (σ0). The crystalline phase polymorphs of the materials (tetragonal, t, and monoclinic, m, zirconia) were investigated by X-ray diffraction (XRD) analysis, Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy., Results: A slight increase of the flexural strength after 5h, and a decrease after 10h of aging, was recorded for both ceramics, however statistically significant was for the WI group (P<0.05). Both ceramics presented a t→m phase transformation, with the m-phase increasing from 4 to 5% at 5h to around 15% after 10h., Significance: The significant reduction of the flexural strength after 10h of in vitro aging, suggests high fracture probability for one of the zirconia ceramics tested., (Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Novel Carbon Nanotube-Polymer Hybrids were synthesized as potential materials for the development of membranes for water treatment applications in the field of Membrane Bioreactors (MBRs). Due to the toxicological concerns regarding the use of nanomaterials in water treatment as well as the rising demand for safe drinking water to protect public health, we studied the functionalization of MWCNTs and Thin-MWCNTs as to control their properties and increase their ability of embedment into porous anisotropic polymeric membranes. Following the growth of the hydrophilic monomer on the surface of the properly functionalized CNTs, that act as initiator for the controlled radical polymerization (ATRP) of sodium styrene sulfonate (SSNa), the antimicrobial quaternized phosphonium and ammonium salts were attached on CNTs-g-PSSNa through non-covalent bonding. In another approach the covalent attachment of quaternized ammonium polymeric moieties of acrylic acid-vinyl benzyl chloride copolymers with N,N-dimethylhexadecylamine (P(AA12-co-VBCHAM)) on functionalized CNTs has also been attempted. Finally, the toxicological assessment in terms of cell viability and cell morphological changes revealed that surface characteristics play a major role in the biological response of functionalized CNTs.

We examine the application of an oscillating cell in combination with right-angle Raman scattered light collection geometry for quantitative Surface Enhanced (Resonance) Raman Scattering (SER(R)S) measurements from nano-colloidal noble metal solutions. This excitation/collection Raman configuration allows specific SERS and SERRS signatures of aqueous solutions of mitoxantrone, an antitumor drug, to be easily resolved at (sub)-ng/mL and (sub)-pg/mL concentration levels. A partial least-squares (PLS) chemometric algorithm was applied to predict the concentration of 25 microL of aqueous solutions of mitoxantrone added in 0.5 mL of a silver colloidal solution in a test tube attached to the oscillating cell. For SERS (514.5 nm) measurements, this was performed over the range from 0 to 13 ng/mL with a correlation coefficient R(2) of 98.5% and RMS error of prediction equal to 0.5 ng/mL. SERRS (632.8 nm) measurements performed over a range of 0 to 7 pg/mL gave R(2) = 98.92% and RMSE = 0.2 pg/mL.

The incorporation of small molecular weight active agents into polymeric matrixes bearing controlled release characteristics represents an interesting strategy with numerous useful applications. Antimicrobials, biocides, fungicides or drugs, encapsulated into erodible or non-erodible polymeric micro-spheres, micro-capsules and micro-shells or/and embedded into continuous polymeric matrixes, are controlled released either by particular degradation routes or/and by specific stimuli. Cross-linking, curing or micro-porosity generating agents acting during polymerization impart additional controlled encapsulation characteristics to the active substances. Release modulating agents, like retardants or carrier materials used as vehicles are often encapsulated into microspheres or dispersed within polymeric compositions for the controlled introduction of an active agent into a liquid-based medium. The aim of this review is to reveal relevant strategies reported in recent patents on the encapsulation or incorporation of low molecular weight active agents into the matrix of polymers bearing controlled release characteristics. The inventions described implicate the formation of both erodible and non erodible polymer microparticles that contain active ingredients. Modification of polymer matrix and inorganic porous carriers represent pertinent major strategies that have been also developed and patented.

We examine the application of an improved noncontact and noninvasive Raman spectroscopic technique in measuring medicines at therapeutic concentrations in a model system mimicking the anterior chamber of the eye. A 90-deg laser Raman scattering geometry is employed to reduce the direct exposure of the basic cordial ocular tissues to the laser beam and increase the signal-to-noise ratio of the spectra. The technique is applied to a commercially available artificial anterior chamber (AAC) fitted with corneas of porcine eyes. Specific Raman signatures of ciprofloxacin (Ciproxin, a fluoroquinolone based antibiotic, have been resolved. Last, a partial least-squares (PLS) chemometric algorithm has been developed to predict the concentration of ciprofloxacin in AAC over the range from 0 to 1 mgmL with a correlation coefficient R(2)=98.4% and an RMS error of prediction equal to 41 microgmL.

Background and Objectives: Laser Raman spectroscopy is an inelastic light scattering technique able to characterize molecules in aqueous environments. The purpose of this work is to develop a non-contact and non-invasive spectroscopic method to identify and eventually quantify the presence of medicines (e.g., antibiotics) and physiological substances (e.g., glucose) in the aqueous humor of the eye., Study Design/materials and Methods: A new laser light delivery probe has been developed and adapted to a Raman spectroscopic system with the ability of favorable collection of the Raman light at 90 degrees scattering geometry while scanning the anterior chamber of the eye. Different amounts of ceftazidime, amphotericin B, and glucose had been injected in the aqueous humor of porcine eyes, maximum 24 hours after death and extraction, in-vitro. Raman measurements were excited with a visible (514.5 nm) laser beam at a power of 25 mW and an exposure/acquisition time of 1 second., Results: The specific collection optics and Raman analysis components used in the present work have resolved the Raman signatures of probed molecules and low concentrations of ceftazidime (0.9 mg/mL), amphotericin B (9 microg/mL), and glucose (2 mg/ml) separately injected in the anterior chamber of porcine eyes were detected in vitro., Conclusion: This special illumination design gives the opportunity of avoiding the direct exposure to the laser light of basic cordial tissues of the eye, like lens and retina, although an optimum collection of scattered light is accomplished. Concentrations close to the minimum inhibitory concentration (MIC) have been detected for ceftazidime and amphotericin b; the detection of glucose has been realized at concentrations close to the early pathological levels of patients with diabetes., (Copyright 2006 Wiley-Liss, Inc.)

Poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) samples uniaxially drawn above Tg and beyond the yield point exhibit significant differences in their molecular orientation behavior as probed by polarized Raman spectra. The quasi-amorphous PET samples, drawn close to the Tg, manifest considerable molecular orientation development; however, when drawn above Tg + 30 degrees C, they exhibit significant molecular orientation relaxation. The semi-crystalline PBT samples maintain prominent molecular orientation even when drawn 110 degrees C above Tg. The drawing process, in PET samples, when resulting in molecular orientation, is accompanied by a gauche-trans transformation of the glycol linkage and a concurrent initiation of crystallinity development. In PBT specimens, it gives rise to a coexistence of alpha- and beta-type crystalline phases. Phase alpha is predominant at high draw temperatures, i.e., Tg + 110 degrees C, while phase beta dominates at low draw temperatures, i.e., Tg + 10 degrees C. PBT samples, with beta-phase predominance, left at relevant draw temperatures without stress, exhibit a beta-alpha phase change though no molecular orientation relaxation occurs. A note is made of the fact that complete molecular orientation analysis of PBT segments utilizing the depol method gives more reliable results than the simplified analysis assuming a cylindrical tensor for the 1614 cm(-1) symmetric stretch of the para-disubstituted benzene ring of PBT. In this context, segments of PBT specimens rich in alpha-phase exhibit higher molecular orientation than those with beta-phase predominance.

A new method of controlled release of low molecular weight biocides incorporated in polymer matrixes is described. The molecular orientation of uniaxially drawn biocide doped polymer films is suggested as a significant parameter for controlled release monitoring. Triclosan, a well-established widespread antibacterial agent, has been incorporated into high density polyethylene (HDPE) films that have been subsequently uniaxially drawn at different draw ratios. The molecular orientation developed was estimated utilizing polarized mu-Raman spectra. Biocide incorporated polymer films, drawn at different draw ratios, have been immersed in ethanol-water solutions (EtOH) and in physiological saline. The release of Triclosan out of the polymer matrix was probed with UV-Vis absorption spectroscopy for a period of time up to 15 months. In all cases, although the film surface of the drawn samples exposed to the liquid solution was higher than the undrawn one, the relevant release rate from the drawn specimens was lower than the non-stretched samples depending on the molecular orientation developed during the drawing process. A note is made of the fact that no significant molecular orientation relaxation of the polyethylene films has been observed even after such a long time of immersion of the drawn films in the liquid solutions.

Triclosan and phosphonium salt biocides have been separately incorporated into polystyrene-divinylbenzene (PS-DVB) beads by suspension polymerization. Ultraviolet (UV) absorption measurements have been used to monitor the release of these low molecular weight biocides out of the PS-DVB beads immersed in water-ethanol mixtures and in physiological saline. The release of the biocide agents is strongly dependent on either the DVB or/and the antimicrobial composition ratio in the beads. An increase of biocide incorporation in the PS/DVB beads was accompanied by a corresponding enhancement of its concentration in liquid mixtures. On the contrary, higher cross-linking densities hindered the biocide migration out of the beads by diminishing its release rate into either the aqueous ethanol solutions or the natural serum. Moreover, Fourier transform Raman (FT-Raman) spectra and Attenuated Total Reflectance Infrared (ATR-FTIR) measurements of the PS-DVB-Triclosan and PS-DVB-phosphonium salt beads, before and after their immersion in water-ethanol solutions, gave a similar qualitative evidence of the biocide release.

A CoMo/gamma-Al(2)O(3) catalyst, prepared by depositing on the Al(2)O(3) carrier first the Mo species via equilibrium deposition filtration (EDF) and then the Co species by dry impregnation, was compared to three CoMo/gamma-Al(2)O(3) samples prepared using various conventional impregnation methods. All samples had the same composition, corresponding to an atomic ratio Co/(Co+Mo) equal to 0.3. The above samples were characterized using various physicochemical techniques (AAS, BET, DRS, LRS, XPS, TPR, and NO chemisorption), and their catalytic activity was determined using the hydrodesulfurization (HDS) of thiophene as a probe reaction. The EDF-prepared catalyst was about 30-43% more active in HDS than those prepared with the conventional impregnation techniques at all reaction temperatures studied. In contrast, the EDF catalyst exhibited the lowest hydrogenation activity. The higher HDS activity of the EDF sample is attributed to the higher number of active HDS sites formed on its surface. It is concluded that the increased number of active sites is due to the fact that the deposition of the Mo species by EDF results to a higher coverage of the support surface by supported molybdenum phase, which in turn, inhibits the formation of the catalytically inactive CoAl(2)O(4) and favors the dispersion of octahedral cobalt on its surface.