On the Structure and Role of Avian Eggshells: A P, H, and C Solid-State NMR Study.

The eggshell is a composite and highly ordered structure formed by biomineralization. Besides other functions, it has a vital and intricate role in the protection of an embryo from various potentially harsh environmental conditions. Solid-state nuclear magnetic resonance (SSNMR) has been used for detailed structural investigations of the chicken, tinamou, and flamingo eggshell materials.

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 (SiO).

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.

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.

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.

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 (MCA)) 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 (MCA) in phosphate buffered saline (PBS, pH 7.

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.

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.

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.

"114"-Type Nitrides LnAl(Si Al )N O with Unusual [AlN ] Octahedral Coordination.

Aluminum-nitrogen six-fold octahedral coordination, [AlN ], 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(Si Al )N O (Ln=La, Sm), the first inorganic compounds with [AlN ] 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 P6 mc symmetry where Ln and Al atoms locate in anticuboctahedral and octahedral interstitials, respectively, between the triangular and Kagomé layers of [SiN ] tetrahedra.

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.

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.

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.

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).

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.

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.

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.

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.

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.

Effect of milling conditions on the solid-state conversion of ranitidine hydrochloride form 1.

Powder samples of ranitidine hydrochloride forms 1 and 2 were milled using a vibrational ball mill (Retsch MM301) for periods up to 240min at 4, 12 and 35 degrees C. X-ray powder diffraction (XRPD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), solid-state nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC) were used to monitor solid-state properties of the milled samples. Milling of form 1 at 4 degrees C led to a powder temperature of 36 degrees C in the milling chamber and produced only amorphous drug; at 12 degrees C (powder temperature 45 degrees C) and at 35 degrees C (powder temperature 62 degrees C) progressive transformation of form 1 via amorphous drug to form 2 occurred.

Fast proton spin-lattice relaxation time in the rotating frame during the application of time averaged precession frequency.

A relatively rapid phase alternation of the effective field in the time averaged precession frequency (TAPF) sequence results in averaging of the proton RF spin-lock field. The spin-locking of the proton magnetization becomes less efficient and thus shortens T(1rho)(H), the proton spin-lattice relaxation time in the rotating frame. The relaxation time also depends on the ratio of tau(1) and tau(2) intervals i.

Transient oscillations under strongly mismatched Hartmann-Hahn conditions.

Based on the standard 2D Polarization inversion experiment, a new pulse sequence (PI-TAPF) is proposed. It represents a combination of Polarization Inversion and TAPF (time averaged precession frequency) sequences. The depolarization period consists of phase-alternating intervals of different duration in the I channel.

Discontinuities in the temperature function of transmembrane water transport in Chara: relation to ion transport.

The NMR (nuclear magnetic resonance) method of Conlon and Outhred (1972) was used to measure diffusional water permeability of the nodal cells of the green alga Chara gymnophylla. Two local minima at 15 and 30 degreesC of diffusional water permeability (Pd) were observed delimiting a region of low activation energy (Ea around 20 kJ/mol) indicative of an optimal temperature region for membrane transport processes. Above and below this region water transport was of a different type with high Ea (about 70 kJ/mol).