Preparation of double emulsions using hybrid polymer/silica particles: New pickering emulsifiers with adjustable surface wettability

A facile route for the preparation of water-in-oil-in-water (w/o/w) double emulsions is described for three model oils, namely, n-dodecane, isopropyl myristate, and isononyl isononanoate, using fumed silica particles coated with poly(ethylene imine) (PEI). The surface wettability of such hybrid PEI/silica particles can be systematically adjusted by (i) increasing the adsorbed amount of PEI and (ii) addition of 1-undecanal to the oil phase prior to homogenization. In the absence of this long-chain aldehyde, PEI/silica hybrid particles (PEI/silica mass ratio = 0.50) produce o/w Pickering emulsions in all cases. In the presence of 1-undecanal, this reagent reacts with the primary and secondary amine groups on the PEI chains via Schiff base chemistry, which can render the PEI/silica hybrid particles sufficiently hydrophobic to stabilize w/o Pickering emulsions at 20 °C. Gas chromatography, 1H NMR and X-ray photoelectron spectroscopy provide compelling experimental evidence for this in situ surface reaction, while a significant increase in the water contact angle indicates markedly greater hydrophobic character for the PEI/silica hybrid particles. However, when PEI/silica hybrid particles are prepared using a relatively low adsorbed amount of PEI (PEI/silica mass ratio = 0.075) only o/w Pickering emulsions are obtained, since the extent of surface modification achieved using this Schiff base chemistry is insufficient. Fluorescence microscopy and laser diffraction studies confirm that highly stable w/o/w double emulsions can be achieved for all three model oils. This is achieved by first homogenizing the relatively hydrophobic PEI/silica hybrid particles (PEI/silica mass ratio = 0.50) with an oil containing 3% 1-undecanal to form an initial w/o emulsion, followed by further homogenization using an aqueous dispersion of relatively hydrophilic PEI/silica particles (PEI/silica mass ratio = 0.075). Dye release from the internal aqueous cores into the aqueous continuous phase was monitored by visible absorption spectroscopy. These studies indicate immediate loss of 12-18% dye during the high speed homogenization that is required for double emulsion formation, but no further dye release is observed at 20 °C for at least 15 days thereafter

Effect of surgical experience and spine subspecialty on the reliability of the {AO} Spine Upper Cervical Injury Classification System

OBJECTIVE The objective of this paper was to determine the interobserver reliability and intraobserver reproducibility of the AO Spine Upper Cervical Injury Classification System based on surgeon experience (< 5 years, 5–10 years, 10–20 years, and > 20 years) and surgical subspecialty (orthopedic spine surgery, neurosurgery, and "other" surgery). METHODS A total of 11,601 assessments of upper cervical spine injuries were evaluated based on the AO Spine Upper Cervical Injury Classification System. Reliability and reproducibility scores were obtained twice, with a 3-week time interval. Descriptive statistics were utilized to examine the percentage of accurately classified injuries, and Pearson’s chi-square or Fisher’s exact test was used to screen for potentially relevant differences between study participants. Kappa coefficients (κ) determined the interobserver reliability and intraobserver reproducibility. RESULTS The intraobserver reproducibility was substantial for surgeon experience level (< 5 years: 0.74 vs 5–10 years: 0.69 vs 10–20 years: 0.69 vs > 20 years: 0.70) and surgical subspecialty (orthopedic spine: 0.71 vs neurosurgery: 0.69 vs other: 0.68). Furthermore, the interobserver reliability was substantial for all surgical experience groups on assessment 1 (< 5 years: 0.67 vs 5–10 years: 0.62 vs 10–20 years: 0.61 vs > 20 years: 0.62), and only surgeons with > 20 years of experience did not have substantial reliability on assessment 2 (< 5 years: 0.62 vs 5–10 years: 0.61 vs 10–20 years: 0.61 vs > 20 years: 0.59). Orthopedic spine surgeons and neurosurgeons had substantial intraobserver reproducibility on both assessment 1 (0.64 vs 0.63) and assessment 2 (0.62 vs 0.63), while other surgeons had moderate reliability on assessment 1 (0.43) and fair reliability on assessment 2 (0.36). CONCLUSIONS The international reliability and reproducibility scores for the AO Spine Upper Cervical Injury Classification System demonstrated substantial intraobserver reproducibility and interobserver reliability regardless of surgical experience and spine subspecialty. These results support the global application of this classification system

Encapsulation of living cells into sporopollenin microcapsules

We demonstrate that living cells can be encapsulated inside sporopollenin microcapsules derived from Lycopodium clavatum. To encapsulate large objects like cells, the sporopollenin particles are compressed into a pellet which forces their trilite scars to open up. Our method involves exposing a sporopollenin pellet to an aqueous suspension of cells in the presence of a surface active agent which facilitates the capillary suction of the cells suspension inside the compressed sporopollenin and its “re-inflating” and closure of trilite scars. We demonstrate that the viability of the cells is preserved after the encapsulation in the sporopollenin capsules which contain a significant amount of entrapped cells and show biological activity when placed into a culture medium. Since the sporopollenin nanopores allow nutrient transport across the capsule wall, it could be used for controlling the rate of in situfermentation reactions or as bio-reactors. We also show that sporopollenin can be loaded with magnetic nanoparticles and live cultures simultaneously which would allow remote manipulation, fixation, removal or potentially targeted delivery of such bio-microreactors. The encapsulation of living cells inside sporopollenin can be used for many different purposes in the food and pharmaceutical industries, including protection of probiotics in foods and delivery of live vaccines for pharmaceutical applications

FTIR spectral band shifts explained by OM–cation interactions

BACKGROUND: The organic matter (OM) in soils interacts with polyvalent cations such as Ca2+ through hydroxyl (OH), carboxylic acid, ester, keto, aldehyde (summarized as C=O), and carboxylate (COO−) functional groups. Such interactions affect the bonding strength of the double bond between the C and the O atom in the functional groups, which is assumed to shift the wavenumber (WN) region of O–H (hydroxyl), C=O, COO−, and OMcat (i.e., C=O interacting with cations plus O–H groups) absorption band maxima in the Fourier transform infrared (FTIR) spectra. Such band shifts limit the evaluation of spectral information on OM in soil samples. AIMS: The objective of this study was to analyze the extent of band shifts and the changes in absorption band intensities for relations with cation concentrations, and to estimate effects of band shifts on OM properties such as potential wettability of OM evaluated from FTIR absorption band ratios. METHODS: Polygalacturonic acid (PGA) solutions were mixed with a CaCl2 solution at different relations. The freeze-dried mixtures were analyzed with FTIR spectroscopy in the mid-infrared spectral range by using KBr-technique. The FTIR spectra were interpreted with respect to O–H, C=O, COO−, and OMcat bands, the latter reflecting the formation of PGA-Ca2+ complexes. RESULTS: The FTIR spectra of the PGA–Ca mixtures compared to that of pure PGA indicate band shift effects by CaCl2 addition on both, intensity and WN value of the OMcat, C=O and COO− absorption band maxima. The COO−/C–O–C ratio increased with Ca2+ concentration while the C–H/C–O–C ratio decreased. Furthermore, the C=O and COO− absorption band maxima were shifted towards lower WN values, while the OMcat absorption band was shifted towards higher WN values. The shift of OMcat band maxima was two times higher than that of the C=O band maximum and increased with Ca2+ concentration. CONCLUSION: Spectral band shifts depend on polyvalent cation concentration and limit automated interpretations of FTIR spectra without prior soil-specific spectral corrections