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.     

Eugenol,citral, and hexanal,alone or in combination with heat,affect viability,biofilm formation,and swarming on Shiga-toxin-producing Escherichia coli

Shiga-toxin-producing Escherichia coli strains are pathogenic for humans and cause mild to severe illnesses. In this study, the antimicrobial effect of citral, eugenol, and hexanal in combination with heat shock (HS) was evaluated in terms of the growth, biofilm formation, swarming, and expression of virulence genes of STEC serotypes (O157:H7, O103, O111, and O26). Eugenol was the most effective compound against the growth of E. coli strains (MBC = 0.58 to 0.73 mg/mL), followed by citral (MBC = 0.86 to 1.26 mg/mL) and hexanal (MBC = 2.24 to 2.52 mg/mL). Biofilm formation and swarming motility have great variability between STEC strains. Natural compounds—alone or combined with HS—inhibited biofilm formation; however, swarming motility was induced by most treatments. The expression of the studied genes during biofilm formation and swarming under natural antimicrobials was affected but not in a uniform pattern. These treatments could be used to control contamination of STEC and inhibit biofilm formation.     

The use of joint coordinates to monitor patients in a movement-based interaction system

Universal Access in the Information Society - Movement-based interaction has brought about new possibilities in healthcare environments. Concretely, rehabilitation therapies represent an adequate...     

Measurements and modeling of absorptive partitioning of volatile organic compounds to painted surfaces

Partitioning to surfaces is an important sink for volatile organic compounds (VOCs) indoors, but the mechanisms are not well understood or quantified. Here, a mass spectrometer was coupled to a portable surface reactor and a flow tube to measure partitioning of VOCs into paint films coated onto glass or wallboard, and their subsequent diffusion. A model was developed to extract values of the effective absorbing organic mass concentration of the film, C_w, which is a measure of absorption capacity, and VOC diffusion coefficients, D_f, from VOC time profiles measured during film passivation and depassivation. Values of C_w agreed well with the value estimated from the paint film mass and flow tube air volume, and D_f values (also measured using attenuated total reflectance-Fourier transform infrared spectroscopy) correlated well with VOC vapor saturation concentrations, C*, estimated using a group contribution method. The value of these relationships for estimating key parameters that control VOC partitioning into paint and the fate of VOCs indoors was demonstrated using a house model, which indicated that >50% of VOCs with C* ≤10⁸ μg/m³ (C* of octane, hexanone, and propanol) that contacted a paint film of typical thickness fully permeated the film regardless of emission duration.     

New ways to improve the damping properties in high‐performance thermoplastic vulcanizates

The incorporation of viscoelastic materials represents an effective strategy to reduce the vibratory level of structural components. Thermoplastic vulcanizates (TPVs) are a special type of viscoelastic material that combines the elastomeric properties of rubbers with the easy processing of thermoplastics. In the present work, we propose innovative ways to improve the damping properties of high‐performance TPVs by using rubbers with carboxylic functionalities. For that, TPVs from physical blends of carboxylated hydrogenated acrylonitrile butadiene rubber (XHNBR) and polyamide 6 (PA6) were prepared. The chain dynamics of different mixed crosslink systems containing peroxide, metal oxides and hindered phenolic antioxidants were investigated in order to find the most suitable strategy to design a high‐performance TPV system with upgraded damping properties. The results indicate that the damping performance of the TPV system can be tailored by controlling the type and magnitude of the bonding interactions between the mixed crosslink system and the XHNBR rubber phase. Therefore, this study demonstrates the potential of TPV systems containing carboxylic rubbers as high‐performance damping materials. © 2020 Society of Chemical Industry     

Price competition between a macrocell and a small-cell service provider with limited resources and optimal bandwidth user subscription: a game-theoretical model

The ever-increasing demand for higher data rates in wireless commutations provides a rationale for small cells deployment. While the physical and technological aspects of small-cell networks have been extensively studied in recent years, the economic analysis has received much less attention. We focus on the economic rationale for a small-cell service provider (SSP) operating a market where an incumbent macrocell service provider (MSP) exists, and competition develops. We analyze such scenario for the case of fixed users by means of Game Theory, specifically through a two-stage game: in the first stage each service provider posts its price according to a Stackelberg game where the MSP is the leader and the SSP is the follower; and, in the second stage, each user chooses both which provider to subscribe to and the optimal amount of bandwidth. A subgame perfect Nash equilibrium is used as a solution concept, and it is derived analytically. We show that the SSP has an incentive to operate in the market and its profit gets higher as SSP’s resources increase. Furthermore, users benefit from SSP’s operation, which may provide a rationale for a regulatory authority to grant the SSP access to the market, despite the fact that MSP’s profit is harmed. Finally, we identify two modes of operation of the system, which depend on the SSP coverage: one where SSP’s deployment is limited and the MSP strategy is not affected by SSP competition and takes only the users outside the SSP coverage; and another, where the SSP covers a large area and the MSP competes against the SSP taking a fraction of the users inside the small cells.     

Progress in the design of zeolite catalysts for biomass conversion into biofuels and bio-based chemicals

This article reviews the recent advances in the development of zeolite catalysts for biomass valorization processes to produce both biofuels and/or bio-based chemicals, which is an emerging and fast expanding field. The work deals with different types of feedstocks, including vegetable oils, lignocellulose and sugars, as well as with a number of relevant intermediates and platform molecules. Transformation of biomass into valuable products is hindered by a number of factors, mainly related to its complex composition, as biomass typically consists of bulky molecules with high oxygen content. Accordingly, biomass processing usually requires the combination of multiple steps and severe conditions, hence concepts like atom efficiency, product selectivity, and catalyst deactivation become of special relevance. A great progress has been achieved in the past years engineering the properties of zeolites for being adapted to the challenges associated to biomass valorization. The possibility of tailoring the main physicochemical properties of zeolites has become now a reality, being the major reason that explains the success achieved by this class of materials in a growing variety of biomass conversion pathways, as those described in this work: catalytic cracking and pyrolysis, hydrotreatments, with special relevance for hydrodeoxygenation processes, as well as in a high number of condensation, isomerization, and dehydration reactions. Thus, the development of hierarchical zeolites, exhibiting enhanced accessibility, and the possibility of introducing and combining in a controlled way different types of active sites (Brønsted and Lewis acid centers, basic sites, and metal phases) are the main basis of the excellent performance of zeolites in numerous biomass conversion routes.     

Synthesis and SAR of Tetracyclic Inhibitors of Protein Kinase CK2 Derived from Furocarbazole W16

The serine/threonine kinase CK2 modulates the activity of more than 300 proteins and thus plays a crucial role in various physiological and pathophysiological processes including neurodegenerative disorders of the central nervous system and cancer. The enzymatic activity of CK2 is controlled by the equilibrium between the heterotetrameric holoenzyme CK2α₂β₂ and its monomeric subunits CK2α and CK2β. A series of analogues of W16 ((3aR,4S,10S,10aS)-4-{[(S)-4-benzyl-2-oxo-1,3-oxazolidin-3-yl]carbonyl}-10-(3,4,5-trimethoxyphenyl)-4,5,10,10a-tetrahydrofuro[3,4-b]carbazole-1,3(3aH)-dione ((+)- 3 a )) was prepared in an one-pot, three-component Levy reaction. The stereochemistry of the tetracyclic compounds was analyzed. Additionally, the chemically labile anhydride structure of the furocarbazoles 3 was replaced by a more stable imide ( 9 ) and N-methylimide ( 10 ) substructure. The enantiomer (−)- 3 a (K_i=4.9 μM) of the lead compound (+)- 3 a (K_i=31 μM) showed a more than sixfold increased inhibition of the CK2α/CK2β interaction (protein-protein interaction inhibition, PPII) in a microscale thermophoresis (MST) assay. However, (−)- 3 a did not show an increased enzyme inhibition of the CK2α₂β₂ holoenzyme, the CK2α subunit or the mutated CK2α′ ^C336S subunit in the capillary electrophoresis assay. In the pyrrolocarbazole series, the imide (−)- 9 a (K_i=3.6 μM) and the N-methylimide (+)- 10 a (K_i=2.8 μM) represent the most promising inhibitors of the CK2α/CK2β interaction. However, neither compound could inhibit enzymatic activity. Unexpectedly, the racemic tetracyclic pyrrolocarbazole (±)- 12 , with a carboxy moiety in the 4-position, displays the highest CK2α/CK2β interaction inhibition (K_i=1.8 μM) of this series of compounds.     

Physicochemical and technological properties of beef burger as influenced by the addition of pea fibre

This study aimed to evaluate the physicochemical characteristics and sensory attributes of beef burgers with the addition of pea fibre as a partial substitute of meat or fat. Three formulations were prepared: control (CON) – similar to the commercial formulation; fibre/less meat (FLM)—5% meat reduction and addition of 1% pea fibre; fibre/less fat (FLF)—7% fat reduction and addition of 1% pea fibre. Non-significant differences were obtained for pH, colour parameters (L* and b*), texture profile, cooking loss and size reduction among formulations. Moreover, sensory analysis with consumers of beef burgers did not indicate differences among the formulations for all the analysed attributes. Therefore, pea fibre is a promising partial replacer for meat and fat in beef burgers due to the preservation of technological parameters and sensory acceptance.     

Proteome changes in lamb semimembranosus muscles associated with the inclusion of sunflower cake in their diet

A diet based on sunflower cake for lambs was assayed in order to reuse biodiesel industrial by-products with the aim of reducing livestock costs and evaluating their influence on meat quality. To achieve these goals, sixteen male lambs were fed diets containing different levels of sunflower cake (control, 5%, 10% and 15%). Afterwards, their semimembranosus muscles were analysed by two-dimensional electrophoresis coupled to mass spectrometry and their functional protein association was examined using STRING. Structural and metabolic proteins in the lambs’ proteomes changed significantly according to their diet. Fifteen proteins showed significant changes caused by the inclusion of sunflower cake, and the most differentially abundant structural proteins were detected in 2-DE gels from the lambs. Differentially abundant metabolic proteins such as ENO3 (enolase 3), MDH1 (malate dehydrogenase) and ALDH1A1 (retinal dehydrogenase) have been proposed as biomarkers of quality parameters in other species.