Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Synthesis and characterization of a pyrochlore solid solution in the Na2O-Bi2O3-TiO2 system

The compositional limits of a previously reported (J. Am. Ceram. Soc., 61, 5-8. (1978)) but relatively unstudied sodium-bismuth titanate pyrochlore solid solution are revised and their electrical properties presented. The pyrochlore solid solution we report forms via a different mechanism to that originally reported and occurs in a different location within the Na₂O-Bi₂O₃-TiO₂ ternary system. In both cases, relatively large amounts of vacancies are required on the A-sites and on the oxygen sites, similar to that reported for undoped ‘Bi₂Ti₂O₇’ pyrochlore. In contrast to ‘Bi₂Ti₂O₇’, this ternary pyrochlore solid solution can be prepared and ceramics sintered using conventional solid-state methods; however, the processing requires several challenges to be overcome to obtain dense ceramics. This cubic pyrochlore series has low electrical conductivity (and does not exhibit any evidence of oxide-ion conduction) and exhibits relaxor ferroelectric behavior with a broad permittivity maximum of ~100 near room temperature. Variable temperature neutron diffraction data do not provide any conclusive evidence for a phase transition in the pyrochlore solid solution between ~4 and 873 K.     

Finite element modeling of resistive surface layers by micro-contact impedance spectroscopy

Micro-contact impedance spectroscopy (MCIS) is potentially a powerful tool for the exploration of resistive surface layers on top of a conductive bulk or substrate material. MCIS employs micro-contacts in contrast to conventional IS where macroscopic electrodes are used. To extract the conductivity of each region accurately using MCIS requires the data to be corrected for geometry. Using finite element modeling on a system where the resistivity of the surface layer is at least a factor of ten greater than the bulk/substrate, we show how current flows through the two layers using two typical micro-contact configurations. This allows us to establish if and what is the most accurate and reliable method for extracting conductivity values for both regions. For a top circular micro-contact and a full bottom counter electrode, the surface layer conductivity (σ_s) can be accurately extracted using a spreading resistance equation if the thickness is ~10 times the micro-contact radius; however, bulk conductivity (σ_b) values can not be accurately determined. If the contact radius is 10 times the thickness of the resistive surface, a geometrical factor using the micro-contact area provides accurate σ_s values. In this case, a spreading resistance equation also provides a good approximation for σ_b. For two top circular micro-contacts on thin resistive surface layers, the MCIS response from the surface layer is independent of the contact separation; however, the bulk response is dependent on the contact separation and at small separations contact interference occurs. As a consequence, there is not a single ideal experimental setup that works; to obtain accurate σ_s and σ_b values the micro-contact radius, surface layer thickness and the contact separation must all be considered together. Here we provide scenarios where accurate σ_s and σ_b values can be obtained that highlight the importance of experimental design and where appropriate equations can be employed for thin and thick resistive surface layers.     

Expression of Main Toll-Like Receptors in Patients with Different Types of Colorectal Polyps and Their Relationship with Gut Microbiota

Abnormal activation of Toll-like receptor (TLRs) signaling can result in colon cancer development. The aim of this study was to investigate the expression of important TLRs in different histological types of colorectal polyps and evaluate their relationship with intestinal microbiota. The expression levels of TLR2, 3, 4, and 5 were analyzed in intestinal biopsy specimens of 21 hyperplastic polyp (HP), 16 sessile serrated adenoma (SSA), 29 tubular adenoma (TA), 21 villous/tubulovillous (VP/TVP) cases, and 31 normal controls. In addition, selected gut bacteria including Streptococcus bovis, Enterococcus faecalis, Enterotoxigenic Bacteroides fragilis (ETBF), Fusobacterium nucleatum, Porphyromonas spp., Lactobacillus spp., Roseburia spp., and Bifidobacterium spp. were quantified in fecal samples using absolute qRT PCR, and, finally, the association between TLRs and these gut microbiota- was evaluated by Spearman’s correlation coefficient. Higher expression of TLR2 and TLR4 in VP/TVP and TA, and lower expression levels of TLR3 and TLR5 in all type of polyps were observed. The differences in TLR expression patterns was not only dependent on the histology, location, size, and dysplasia grade of polyps but also related to the intestinal microbiota patterns. TLR2 and TLR4 expression was directly associated with the F. nucleatum, E. faecalis, S. bovis, Porphyromonas, and inversely to Bifidobacterium, Lactobacillus, and Roseburia quantity. Furthermore, TLR3 and TLR5 expression was directly associated with Bifidobacterium, Roseburia, and Lactobacillus quantity. Our results suggest a possible critical role of TLRs during colorectal polyp progression. An abnormal regulation of TLRs in relation to gut microbial quantity may contribute to carcinogenesis.     

Conversion of natural gas jet flame burners to hydrogen

In a study of conversion from CH₄ to H₂, jet flame characteristics of these gases and their blends are compared on a burner diameter scale of mm. Low velocity H₂ and CH₄ jets, burned on pipes of different diameters, indicate higher blow-off limits for H₂, but lower heat release rates, a consequence of its lower specific energy. Compensation for this might be obtained through increased H₂ flow velocity, or a small increase in pipe diameter. Blended CH₄/H₂ flames have lower heat release rates than CH₄ alone, yet small proportions of H_2, with CH₄ might still be burned, on a CH₄ burner. Throughout, fundamental understanding is enhanced through two dimensionless groups: laminar flame thickness normalised by burner diameter, δ_k/D, and the dimensionless flow number, U1. These suggest an optimal role for H₂ combustion, utilizing its high acoustic and blow-off velocities, in high intensity, subsonic, combustors, at low δ_k/D, and high U1.     

Enhancing the stability and crystallinity of CsPbIBr2 through antisolvent engineering

All inorganic lead-based perovskites containing bromine-iodine alloys, such as CsPbIBr_2, have arisen as one of the most attractive candidates for absorber layers in solar cells. That said, there remains a large gap when it comes to film and crystal quality between the inorganic and hybrid perovskites. In this work, antisolvent engineering is employed as a simple and reproducible method for improving CsPbIBr₂ thin films. We found that both the antisolvent used and the conditions under which it was applied have a measurable impact on both the quality and stability of the final product. We arrived at this conclusion by characterising the samples using scanning electron microscopy, X-ray diffraction, UV–visible and photoluminescence measurements, as well as employing a novel system to quantify stability. Our findings, and the application of our novel method for quantifying stability, demonstrate the ability to significantly enhance CsPbIBr₂ samples, produced via a static one-step spin coating method, by applying isopropanol 10 s after commencing the spin programme. The antisolvent quenched CsPbIBr₂ films demonstrate both improved crystallinity and an extended lifespan.

     

Bioelectronic protein nanowire sensors for ammonia detection

Electronic sensors based on biomaterials can lead to novel green technologies that are low cost, renewable, and eco-friendly. Here we demonstrate bioelectronic ammonia sensors made from protein nanowires harvested from the microorganism Geobacter sulfurreducens. The nanowire sensor responds to a broad range of ammonia concentrations (10 to 10⁶ ppb), which covers the range relevant for industrial, environmental, and biomedical applications. The sensor also demonstrates high selectivity to ammonia compared to moisture and other common gases found in human breath. These results provide a proof-of-concept demonstration for developing protein nanowire based gas sensors for applications in industry, agriculture, environmental monitoring, and healthcare.

     

A Flexi-PEGDA Upconversion Implant for Wireless Brain Photodynamic Therapy

Near-infrared (NIR) activatable upconversion nanoparticles (UCNPs) enable wireless-based phototherapies by converting deep-tissue-penetrating NIR to visible light. UCNPs are therefore ideal as wireless transducers for photodynamic therapy (PDT) of deep-sited tumors. However, the retention of unsequestered UCNPs in tissue with minimal options for removal limits their clinical translation. To address this shortcoming, biocompatible UCNPs implants are developed to deliver upconversion photonic properties in a flexible, optical guide design. To enhance its translatability, the UCNPs implant is constructed with an FDA-approved poly(ethylene glycol) diacrylate (PEGDA) core clad with fluorinated ethylene propylene (FEP). The emission spectrum of the UCNPs implant can be tuned to overlap with the absorption spectra of the clinically relevant photosensitizer, 5-aminolevulinic acid (5-ALA). The UCNPs implant can wirelessly transmit upconverted visible light till 8 cm in length and in a bendable manner even when implanted underneath the skin or scalp. With this system, it is demonstrated that NIR-based chronic PDT is achievable in an untethered and noninvasive manner in a mouse xenograft glioblastoma multiforme (GBM) model. It is postulated that such encapsulated UCNPs implants represent a translational shift for wireless deep-tissue phototherapy by enabling sequestration of UCNPs without compromising wireless deep-tissue light delivery.