Solvent-Free, Ambient Temperature and Pressure Destruction of Perfluorosulfonic Acids under Mechanochemical Conditions: Degradation Intermediates and Fluorine Fate.

Perfluorosulfonic acids (PFSAs) are a recalcitrant subclass of per- and polyfluoroalkyl substances (PFASs) linked to numerous negative health effects in humans. Scalable technologies that effectively destroy PFSAs will greatly reduce the future health and ecological impact of these "forever chemicals". Herein, we show that several PFSAs undergo facile mechanochemical destruction (MCD) in the presence of quartz sand (SiO2). This process operates in the absence of solvent, at ambient temperature and pressure, generating a benign solid byproduct. Quantitative analysis of milled samples revealed high destruction efficiencies of 99.95% to 100% for five different PFSAs subjected to MCD conditions in the presence of SiO2 only. Extensive nontargeted analysis showed that, during degradation, other PFASs form and are ultimately destroyed upon extended mechanochemical treatment. Direct polarization (DP) and cross-polarization (CP) solid-state nuclear magnetic resonance (SSNMR) spectroscopy showed abundant silicon-fluorine (Si-F) bond formation post-MCD, indicating that fluorine was secured in a stable reservoir. Collectively, these results identified the degradation profile for an environmentally sound and effective PFSA degradation process that is amenable to scale-up.

First use of grape waste-derived building blocks to yield antimicrobial materials.

Grape marc is an underutilised waste material that poses significant environmental issues. This study offers the first proof-of-concept investigation into the polymerisation of both crude and purified Sauvignon blanc grape marc extracts using the diacyl chlorides terephthaloyl chloride, succinyl chloride, adipoyl chloride, sebacoyl chloride, and the tartaric acid derivative (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarbonyl dichloride to obtain new materials, in what to the best of our knowledge is the first reported example of a direct polymerisation of an agricultural waste extract. A total of 26 novel materials were prepared. It has also shown that quercetin, a phenolic monomer found in grape marc extracts, can be polymerised with (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarbonyl dichloride to give a polymer that shows activity towards S. aureus.

The Applications of Solid-State NMR to Conducting Polymers. The Special Case on Polyaniline.

Polyaniline is one of the most well studied conducting polymers due to its advanced electrical, chemical, redox and morphological properties. The high conductivity of regular polyaniline, when partially oxidized and doped under acidic conditions, has been associated with the formation of unique electronic states known as polarons and bipolarons. Alternative aniline oxidation products and interesting nanotube and nanorod forms have been observed as the synthesis conditions are varied. Solid-state NMR has offered great opportunities for structural investigations and the determination of molecular dynamics in such a complex and diverse material. This review summarizes various applications of solid-state NMR techniques to polyaniline and its derivatives and the information that can be obtained by solid-state NMR.

Characterization of an Antioxidant and Antimicrobial Extract from Cool Climate, White Grape Marc.

Valorization of agricultural waste has become increasingly important. Wastes generated by wineries are high in phenolic compounds with antioxidant and antibacterial properties, which contribute to phytotoxicity, making their immediate use for agricultural means limited. Utilizing a water-based extraction method, the phenolic compounds from winery waste were extracted and purified. The resulting extract was characterized for phenolic composition using high-pressure liquid chromatography-ultraviolet/visible and electrochemical detectors (HPLC-UV/Vis, ECD) for monomers, and spectral assessment of the tannins present using attenuated total reflectance- Fourier transform infrared (ATR-FTIR), FT-Raman, and solid-state nuclear magnetic resonance (SSNMR) spectroscopies. The extract's antioxidant activity was assessed by the scavenging of the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and Folin-Ciocalteu total phenolic assay, and was found to be as effective as a commercially obtained grape extract. The extract's antimicrobial efficacy was tested for minimum bactericidal concentration using Candida albicans, Escherichia coli 25922, and Staphylococcus aureus 6538, which resulted in greater efficacy against gram-positive bacteria as shown over gram-negative bacteria, which can be linked to both monomeric and tannin polyphenols, which have multiple modes of bactericidal action.

Crystalline adduct of moxifloxacin with trans-cinnamic acid to reduce the aqueous solubility and dissolution rate for improved residence time in the lungs.

A crystalline adduct of the anti-tubercular drug, moxifloxacin and trans-cinnamic acid (1:1 molar ratio (MCA1:1)) was prepared to prolong the residence time of the drug in the lungs by reducing its solubility and dissolution rate. Whether the adduct is a salt or cocrystal has not been unequivocally determined. Equilibrium solubility and intrinsic dissolution rate measurements for the adduct (MCA1:1) in phosphate buffered saline (PBS, pH 7.4) revealed a significant decrease in the solubility of moxifloxacin (from 17.68 ±â€¯0.85 mg mL-1 to 6.10 ±â€¯0.05 mg mL-1) and intrinsic dissolution rate (from 0.47 ±â€¯0.04 mg cm-2 min-1 to 0.14 ±â€¯0.03 mg cm-2 min-1) compared to the supplied moxifloxacin. The aerosolization behaviour of the adduct from an inhaler device, Aerolizer®, using a Next Generation Impactor showed a fine particle fraction of 30.4 ±â€¯1.2%. The dissolution behaviour of the fine particle dose of respirable particles collected was assessed in a small volume of stationary mucus fluid using a custom-made dissolution apparatus. The respirable adduct particles showed a lower dissolution (microscopic observation) and permeation compared to the supplied moxifloxacin. The crystalline adduct MCA1:1 has a lower solubility and dissolution rate than moxifloxacin and could improve the local residence time and therapeutic action of moxifloxacin in the lungs.

Developmental changes in collenchyma cell-wall polysaccharides in celery (Apium graveolens L.) petioles.

BACKGROUND: Collenchyma cells occur widely in eudicotyledons and provide mechanical support for growing organs. At maturity, the cells are elongated and have thick, non-lignified walls, which in celery contain cellulose and pectic polysaccharides, together with xyloglucans and heteroxylans and heteromannans. A previous study suggested that at least some of the collenchyma cell wall in celery is laid down after expansion has stopped and is thus secondary. In the present study, we re-examined this. We used chemical analysis and immunomicroscopy to determine changes in the polysaccharide compositions of these walls during development. Additionally, solid-state NMR spectroscopy was used to examine changes in polysaccharide mobilities during development. RESULTS: We showed the collenchyma walls are deposited only during cell expansion, i.e. they are primary walls. During cell-wall development, analytical and immunomicroscopy studies showed that within the pectic polysaccharides there were no overall changes in the proportions of homogalacturonans, but there was a decrease in their methyl esterification. There was also a decrease in the proportions of the (1 → 5)-α-L-arabinan and (1 → 4)-ß-D-galactan side chains of rhamnogalacturonan I. The proportions of cellulose increased, and to a lesser extent those of xyloglucans and heteroxylans. Immunomicroscopy showed the homogalacturonans occurred throughout the walls and were most abundant in the middle lamellae and middle lamella junctions. Although the (1 → 4)-ß-D-galactans occurred only in the rest of the walls, some of the (1 → 5)-α-L-arabinans also occurred in the middle lamellae and middle lamella junctions. During development, the location of the xyloglucans changed, being confined to the middle lamellae and middle lamella junctions early on, but later occurred throughout the walls. The location of the heteroxylans also changed, occurring mostly in the outer walls in young cells, but were more widely distributed in mature cells. Solid-state NMR spectroscopy showed that particularly cellulose, but also homogalacturonans, decreased in mobility during development. CONCLUSIONS: Our studies showed that celery collenchyma cell walls are primary and that during their development the polysaccharides undergo dynamic changes. Changes in the mobilities of cellulose and homogalacturonans were consistent with the cell walls becoming stiffer as expansion ceases.

A Sustained Release Anchored Biocide System Utilizing the Honeycomb Cellular Structure of Expanded Perlite.

The development of a sustained-release biocide system, involving an anchored quaternary ammonium salt (AQAS) embedded in expanded perlite (EP) substrate, is reported. Scanning electron microscopy (SEM) images reveal the well-defined honeycomb cells that are a feature of EP. These honeycomb cells exhibit a variety of polygon shapes, which are filled with the AQAS molecules as evidenced by SEM data. The aqueous leaching of the AQAS from the EP honeycomb cells is monitored by the Fourier transform infrared CH stretching absorbance maxima at 2920 and 2850 cm-1. Solid-state NMR data indicate the formation of three dominant oligomeric forms of the AQAS biocide molecules formed within the EP network by condensation reactions at curing temperatures (160 °C). The various oligomeric species involve different numbers of SiO chains bonded to a central Si atom within the AQAS anchoring groups. Assays confirm the potency of the AQAS oligomers against Staphylococcus aureus and Escherichia coli bacteria.

Polysaccharide compositions of collenchyma cell walls from celery (Apium graveolens L.) petioles.

BACKGROUND: Collenchyma serves as a mechanical support tissue for many herbaceous plants. Previous work based on solid-state NMR and immunomicroscopy suggested collenchyma cell walls (CWs) may have similar polysaccharide compositions to those commonly found in eudicotyledon parenchyma walls, but no detailed chemical analysis was available. In this study, compositions and structures of cell wall polysaccharides of peripheral collenchyma from celery petioles were investigated. RESULTS: This is the first detailed investigation of the cell wall composition of collenchyma from any plant. Celery petioles were found to elongate throughout their length during early growth, but as they matured elongation was increasingly confined to the upper region, until elongation ceased. Mature, fully elongated, petioles were divided into three equal segments, upper, middle and lower, and peripheral collenchyma strands isolated from each. Cell walls (CWs) were prepared from the strands, which also yielded a HEPES buffer soluble fraction. The CWs were sequentially extracted with CDTA, Na2CO3, 1 M KOH and 4 M KOH. Monosaccharide compositions of the CWs showed that pectin was the most abundant polysaccharide [with homogalacturonan (HG) more abundant than rhamnogalacturonan I (RG-I) and rhamnogalacturonan II (RG-II)], followed by cellulose, and other polysaccharides, mainly xyloglucans, with smaller amounts of heteroxylans and heteromannans. CWs from different segments had similar compositions, but those from the upper segments had slightly more pectin than those from the lower two segments. Further, the pectin in the CWs of the upper segment had a higher degree of methyl esterification than the other segments. In addition to the anticipated water-soluble pectins, the HEPES-soluble fractions surprisingly contained large amounts of heteroxylans. The CDTA and Na2CO3 fractions were rich in HG and RG-I, the 1 M KOH fraction had abundant heteroxylans, the 4 M KOH fraction was rich in xyloglucan and heteromannans, and cellulose was predominant in the final residue. The structures of the xyloglucans, heteroxylans and heteromannans were deduced from the linkage analysis and were similar to those present in most eudicotyledon parenchyma CWs. Cross polarization with magic angle spinning (CP/MAS) NMR spectroscopy showed no apparent difference in the rigid and semi-rigid polysaccharides in the CWs of the three segments. Single-pulse excitation with magic-angle spinning (SPE/MAS) NMR spectroscopy, which detects highly mobile polysaccharides, showed the presence of arabinan, the detailed structure of which varied among the cell walls from the three segments. CONCLUSIONS: Celery collenchyma CWs have similar polysaccharide compositions to most eudicotyledon parenchyma CWs. However, celery collenchyma CWs have much higher XG content than celery parenchyma CWs. The degree of methyl esterification of pectin and the structures of the arabinan side chains of RG-I show some variation in the collenchyma CWs from the different segments. Unexpectedly, the HEPES-soluble fraction contained a large amount of heteroxylans.

"114"-Type Nitrides LnAl(Si4-x Alx )N7 Oδ with Unusual [AlN6 ] Octahedral Coordination.

Aluminum-nitrogen six-fold octahedral coordination, [AlN6 ], is unusual and has only been seen in the high-pressure rocksalt-type aluminum nitride or some complex compounds. Herein we report novel nitrides LnAl(Si4-x Alx )N7 Oδ (Ln=La, Sm), the first inorganic compounds with [AlN6 ] coordination prepared via non-high-pressure synthesis. Structure refinements of neutron powder diffraction and single-crystal X-ray diffraction data show that these compounds crystallize in the hexagonal Swedenborgite structure type with P63 mc symmetry where Ln and Al atoms locate in anticuboctahedral and octahedral interstitials, respectively, between the triangular and Kagomé layers of [SiN4 ] tetrahedra. Solid-state NMR data of high-purity La-114 powders confirm the unusual [AlN6 ] coordination. These compounds are the first examples of the "33-114" sub-type in the "114" family. The additional site for over-stoichiometric oxygen in the structure of 114-type compounds was also identified.

Characterisation of waste derived biochar added biocomposites: chemical and thermal modifications.

A step towards sustainability was taken by incorporating waste based pyrolysed biochar in wood and polypropylene biocomposites. The effect of biochar particles on the chemistry and thermal makeup of the composites was determined by characterising them through an array of characterisation techniques such as 3D optical profiling, X-ray diffraction, transmission electron microscopy, electron spin/nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. It was observed that addition of biochar increased the presence of free radicals in the composite while also improving its thermal conductivity. Biochar particles did not interfere with the melting behaviour of polymer in the thermal regime. However, wood and biochar acted as nucleation agents consequently increasing the crystallisation temperature. The crystal structure of polypropylene was not disrupted by biochar inclusion in composite. Transmission electron microscopy images illustrated the aggregated nature of the biochar particles at higher loading levels. Nuclear magnetic resonance studies revealed the aromatic nature of biochar and the broadening of peak intensities of composites with increasing biochar levels due to its amorphous nature and presence of free radicals. Thus, this insight into the chemical and thermal modification of biochar added composites would allow effective engineering to optimise their properties while simultaneously utilising wastes.

Comparison of celery (Apium graveolens L.) collenchyma and parenchyma cell wall polysaccharides enabled by solid-state (13)C NMR.

Collenchyma cells with their thickened walls are one of specific mechanical support tissues for plants, while parenchyma cells are thin walled and serve multiple functions. The parenchyma tissue is what you enjoy eating, while collenchyma, because of its fibrous nature, is not so attractive. Celery is a useful model for comparing the cell walls (CWs) of the two cell types such as collenchyma and parenchyma. However, to date, the structural characteristics of collenchyma and parenchyma cell walls from the same plant have not been compared. Monosaccharide composition suggested the collenchyma cell walls contained less pectin but more hemicellulose in comparison to parenchyma. High-resolution solid-state NMR spectra of highly mobile pectins revealed that the arabinan signals were more evident in the collenchyma spectrum, while galactan showed a much stronger resonance in the parenchyma spectrum. In addition, methyl esterified and non-esterified galacturonic acid signals were observed in parenchyma CWs, but only the latter one appeared in the collenchyma. The ratio of cellulose surface/interior obtained from CP/MAS spectra for collenchyma suggested the cellulose microfibrils were ~2.4 nm, while in the parenchyma, these were somewhat larger. X-ray diffraction indicated the size of the cellulose microfibrils were the same for both types of CWs.

Influence of heat curing on structure and physicochemical properties of phenolic acid loaded proteinaceous electrospun fibers.

Effects of heat treatment on structure and physicochemical properties of zein (Ze) and gallic acid loaded zein (Ze-GA) electrospun fiber mats were investigated. The electrospun fiber mats displayed different surface and physicochemical properties after being heat-cured at 150 °C for 24 h, which were closely related to the initial amount of loaded gallic acid. The gallic acid was released from the Ze-GA fiber mats in a constant manner, but heat curing decreased the rate of release. Heat curing remarkably increased the molecular weight of the Ze and Ze-GA electrospun fiber mats. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis of the fiber mats indicated variations in zein protein secondary structure after heat curing. (13)C solid state NMR (SS-NMR) confirmed the presence of a different chemical environment among the fiber mats. The fabrication of heat-cured zein based electrospun fibers in this study may find applications in the food packaging industry.

Solid-state 13C NMR study of the mobility of polysaccharides in the cell walls of two apple cultivars of different firmness.

Solid-state (13)C nuclear magnetic resonance (NMR) was used to compare differences in mobility of the cell wall polysaccharides of 'Scifresh' and 'Royal Gala' apples after 20 weeks of storage. The texture of 'Scifresh' apples was markedly firmer than that of 'Royal Gala' at the end of storage. In a novel approach Two Pulse Phase Modulation (TPPM) decoupling was combined with cross polarisation (CP) and single pulse excitation (SPE) experiments. The resulting high resolution solid-state SPE spectra, unprecedented for apple cell walls, allowed a detailed insight into the physical and chemical properties of very mobile polysaccharides such as the arabinan and galactan side chains of the pectic polysaccharide rhamnogalacturonan I (RG-I). NMR showed that the cellulose rigidity was the same in the two cultivars, while arabinans were more mobile than galactans in both. Unexpectedly, arabinans in 'Scifresh' cell walls were more mobile than those in 'Royal Gala' which was unforeseen considering the greater firmness of the 'Scifresh' cultivar.

Short range order at the amorphous TiO(2)-water interface probed by silicic acid adsorption and interfacial oligomerization: an ATR-IR and 29Si MAS-NMR study.

Adsorption and oligomerization of H(4)SiO(4) at the amorphous TiO(2)-aqueous interface were studied using in situ Attenuated Total Reflectance Infrared (ATR-IR) and ex situ solid state (29)Si nuclear magnetic resonance (NMR). The ATR-IR spectra indicate that a monomeric silicate species is present at low silicate surface concentration (Γ(Si)). Above a threshold Γ(Si) linear silicate oligomers are formed and these oligomers dominate the surface at high Γ(Si). Interestingly the ATR-IR spectra of H(4)SiO(4) on the TiO(2) surface are very similar to those previously observed on the poorly ordered iron oxide phase ferrihydrite. The (29)Si NMR spectrum of silicate on the TiO(2) surface shows the presence of Si in three states with chemical shifts corresponding to isolated monomers (Q(0)), the ends of linear oligomers (Q(1)) and the middle of linear oligomers (Q(2)). The ratio of the area of the Q(1) and Q(2) peaks was ≈2:1 which is consistent with the proposed formation of linear silicate trimers by insertion of a solution H(4)SiO(4) between adjacent suitably orientated adsorbed silicate monomers. A structural interpretation indicates that the observed interfacial silicate oligomerization behavior is a general phenomenon whereby bidentate silicate monomers on oxide surfaces are disposed towards forming linear oligomers by condensation reactions involving their two terminal Si-OH groups. The high surface curvature of nanometer sized spheres inhibits the formation of interfacial silicates with a higher degree of polymerization.

Evaluation of a crystalline nanosuspension: polymorphism, process induced transformation and in vivo studies.

The aim of this work was to evaluate a crystalline nanosuspension of an investigational anticancer compound, SN 30191. Solid forms of SN 30191 were prepared and characterized by thermal analysis, infrared spectroscopy, ¹³C CP/MAS SSNMR spectroscopy, SEM and powder XRD. Wet milling was performed using a high pressure homogenizer and process induced transformations were studied as a function of time and pressure using infrared spectroscopy. Dose-toxicity and pharmacokinetics (PK) of the nanocrystal formulation were evaluated in mice after intravenous administration. SN 30191 was found to exist in two polymorphic forms (I and II) and a hydrate with an equilibrium solubility < 0.1 µg/ml (pH 1.3-11.0, 37 °C). Wet milling resulted in solid state transformation as a function of pressure. Form II was found to transform into form I at intermediate pressures. A further increase in pressure resulted in formation of a hydrate. The final nanosuspension consisted of SN 30191 as a hydrate. The dose-toxicity studies revealed higher tolerance (~4 times) for the nanosuspension (10 mg/kg) when compared with a solution formulation (2.5 mg/kg). Compared with solution formulation, the nanosuspension allowed the delivery of a higher dose and rendered possible the performance of PK and tissue distribution studies in animals.

Nanostructured aniline oxidation products: self-assembled films at the air/liquid interface.

With the use of the "falling pH" approach, the free floating films obtained at the air/liquid interface during aniline oxidative polymerization in the presence of hydrochloric acid have been reported and characterized for the first time. The surface of the films is compact and consists of small densely packed particles (around 10-20 nm in diameter). In addition to the free floating films the precipitation of various self-assembled nanostructures was also observed. The thickness of the films depends on the concentration of the reactants and ranges from 40 to 50 nm. Scanning electron microscopy (SEM) and transmission electron microscopy results imply that 3D nanostructures are physically adsorbed onto the film and that they represent two separated phases. Fourier transform infrared (FTIR) and UV-vis measurements have confirmed the presence of polyaniline and branched oligoanilines. On the basis of an orientation distribution of H(2)O and aniline molecules at the air/liquid interface and with the use of the cooperative effect of hydrogen-bond formation, a mechanism for film growth has been proposed. Three samples are synthesized in the presence of different acids-nitric, sulfuric, and acetic. The SEM and FTIR data showed similar morphologies and structural characteristics. This implies that the morphology and structure of the final products depend on the acidity conditions (pH) during the reaction rather than on the nature of the dopant acid.

Assessment of crystalline disorder in cryo-milled samples of indomethacin using atomic pair-wise distribution functions.

The aim of this study was to investigate the usefulness of the atomic pair-wise distribution function (PDF) to detect the extension of disorder/amorphousness induced into a crystalline drug using a cryo-milling technique, and to determine the optimal milling times to achieve amorphisation. The PDF analysis was performed on samples of indomethacin obtained by cryogenic ball milling (cryo-milling) for different periods of time. X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), polarised light microscopy (PLM) and solid state nuclear magnetic resonances (ss-NMR) were also used to analyse the cryo-milled samples. The high similarity between the γ-indomethacin cryogenic ball milled samples and the crude γ-indomethacin indicated that milled samples retained residual order of the γ-form. The PDF analysis encompassed the capability of achieving a correlation with the physical properties determined from DSC, ss-NMR and stability experiments. Multivariate data analysis (MVDA) was used to visualize the differences in the PDF and XRPD data. The MVDA approach revealed that PDF is more efficient in assessing the introduced degree of disorder in γ-indomethacin after cryo-milling than MVDA of the corresponding XRPD diffractograms. The PDF analysis was able to determine the optimal cryo-milling time that facilitated the highest degree of disorder in the samples. Therefore, it is concluded that the PDF technique may be used as a complementary tool to other solid state methods and that further investigations are warranted to elucidate the capabilities of this technique.

A rapid and facile synthesis of nanofibrillar polyaniline using microwave radiation.

We present the first fast and facile microwave assisted synthesis of polyaniline (PANI) nanofibers ("MWA synthesis"). Under conventional synthesis (CS), the polymer was produced with 79.7% yield after 5 h at ambient temperature. However, under microwave irradiation, the nanofibers were produced with yield of 76.2% after only 5 min, i.e., with 78.8% after 20 min at ambient temperature. The FTIR and Raman spectra show the PANI structure in all samples either synthesized conventionally or in the microwave. SEM and TEM confirm the nanofibrillar morphology.

Polyaniline "nanotube" self-assembly: the stage of granular agglomeration on nanorod templates.

The identification and control of a critical stage of polyaniline "nanotube" self-assembly is presented, namely the granular agglomeration or growth onto nanorod templates. When the synthesis pH is held above 2.5, smooth insulating nanorods exhibiting hydrogen bonding and containing phenazine structures are produced, while below pH 2.5, small 15-30 nm granular polyaniline nanoparticles appear to agglomerate onto the available nanorod surface, apparently improving conductivity of the resulting structures by three orders of magnitude. This finding affects both fundamental theories of polyaniline nanostructure self-assembly and their practical applications.