Amine Uptake Research Articles

Measurement report: Occurrence of aminiums in PM2.5 during winter in China – aminium outbreak during polluted episodes and potential constraints

Abstract. Amines and aminiums play an important role in particle formation, liquid-phase reactions, and climate change and have attracted considerable attention over the years. Here, we investigated the concentrations and compositions of aminiums in PM2.5 in 11 Chinese cities during the winter, focusing on the characteristics of aminiums during the polluted days and the key factors influencing aminium outbreak. Monomethylaminium was the dominant aminium species in most cities, except Taiyuan and Guangzhou, followed by dimethylaminium. Diethylaminium dominated the total aminiums in Taiyuan and Guangzhou. Thus, the main amine sources in Taiyuan and Guangzhou were significantly different from those in other cities. The concentrations of the total aminiums (TAs) in most cities increased significantly during the polluted days, while relatively weak aminium outbreaks during the polluted days occurred in Xi'an and Beijing. Additionally, the concentrations of TAs in Xi'an and Beijing were insignificantly correlated with those of PM2.5 and the major acidic aerosol components, while the opposite pattern was observed in nine other cities. Thus, acid–base chemistry was significantly associated with the formation of aminiums in PM2.5 in all cities, except Xi'an and Beijing. Based on the sensitivity analysis of the aminiums : ammonium ratio to ammonium changes, as well as excluding the effects of relative humidity and atmospheric oxidation, we proposed the possibility of the competitive uptake of ammonia versus amines on acidic aerosols or the displacement of aminiums by ammonia in Xi'an and Beijing (constraining aminium outbreaks). Overall, this study deepens the understanding of the spatiotemporal differences in aminium characteristic and formation in China. However, the uptake of amines on particles to form aminiums and the relevant influencing factors require further mechanistic research.

Methylamine Separations Enabled by Cooperative Ligand Insertion in Copper-Carboxylate Metal-Organic Frameworks.

Monomethylamine (NH2CH3), dimethylamine (NH(CH3)2), and trimethylamine (N(CH3)3) are important chemical feedstocks that are produced industrially as an azeotropic mixture and must be separated using an energy-intensive thermal distillation. While solid adsorbents have been proposed as alternatives to distillation for separating various industrial gas mixtures, methylamine separations remain largely unexplored in this context. Here, we investigate two isoreticular frameworks Cu(cyhdc) (cyhdc2- = trans-1,4-cyclohexanedicarboxylate) and Cu(bdc) (bdc2- = 1,4-benzenedicarboxylate) as prospective candidates for this challenging separation, motivated by the recent discovery that Cu(cyhdc) reversibly captures ammonia through a unique framework-to-coordination polymer phase change. Through a combination of gas adsorption and powder X-ray diffraction analyses, we find that Cu(cyhdc) and Cu(bdc) reversibly bind large quantities of mono- and dimethylamine through framework-to-coordination polymer phase change mechanisms, although both frameworks adsorb only moderate amounts of trimethylamine via physisorption. Single-crystal X-ray diffraction analysis of select mono- and dimethylamine containing phases suggests that the number of hydrogen bond donors available and the linker donor strength are key factors influencing amine uptake. Finally, investigation of the tricomponent adsorption behavior of both materials reveals that Cu(cyhdc) is selective for the capture of monomethylamine from a range of mono-, di-, and trimethylamine mixtures.

Cooling radiative forcing effect enhancement of atmospheric amines and mineral particles caused by heterogeneous uptake and oxidation

Abstract. The warming radiative forcing effect (RFE) derived from atmospheric amines attracts a lot of attention because of their contribution to brown carbon. Herein, the enhanced influence of amines (methyl-, dimethyl-, and trimethylamine) on cooling RFE of mineral particles is first confirmed at visible wavelengths. Present results state heterogeneous uptake and oxidation reactions of atmospheric amines are feasible on mineral particles under clean and polluted conditions, which are proven by related thermodynamics and kinetics data obtained using combined classical molecular dynamics and density function theory methods. Based on mineral particles, simple forcing efficiency (SFE) results explain that amine uptake induces at least 11.8 %–29.5 % enhancement on cooling RFE of amine–mineral particles at visible wavelengths. After amine heterogeneous oxidation, oxidized amine–mineral particle cooling RFEs are furthermore enhanced due to increased oxygen contents. Moreover, oxidized amine–mineral particles under clean conditions show 27.1 %–47.1 % SFE increments at 400–600 nm, which is at least 11.3 % higher than that of itself under polluted conditions, due to high-oxygen-content product formation through amine autoxidation. Our results suggest cooling RFE derived from atmospheric amines can be equally important to their warming RFE on the atmosphere. It is necessary to update the heterogeneous oxidation mechanism and kinetics data of amines in atmospheric models in order to accurately evaluate the whole RFE caused by amines on the atmosphere.

Effect of Humidity on the Reactive Uptake of Ammonia and Dimethylamine by Nitrogen-Containing Secondary Organic Aerosol

This study investigated the uptake of ammonia (NH3) by secondary organic aerosol (SOA) particles generated via limonene photooxidation or ozonolysis as well as the uptake of dimethylamine (DMA) by limonene ozonolysis, α-cedrene photooxidation, or toluene photooxidation SOA in an environmental chamber between 0–50% relative humidity. In addition to the acid-base equilibrium uptake, NH3 and DMA can react with SOA carbonyl compounds converting them into nitrogen-containing organic compounds (NOCs). The effective reactive uptake coefficients for the formation of NOCs from ammonia were measured on the order of 10−5. The observed DMA reactive uptake coefficients ranged from 10−5 to 10−4. Typically, the reactive uptake coefficient decreased with increasing relative humidity. This is consistent with NOC formation by a condensation reaction between NH3 or DMA with SOA, which produces water as a product. Ammonia is more abundant in the atmosphere than amines. However, the larger observed reactive uptake coefficient suggests that amine uptake may also be a potential source of organic nitrogen in particulate matter.

Highly efficient, reversible iodine capture and exceptional uptake of amines in viologen-based porous organic polymers.

A viologen-based porous organic polymer, POP-V-VI, was designed and synthesized by a facile nucleophilic substitution between cyanuric chloride and 1,2-bis(4-pyridinium) ethylene. Together with the reported POP-V-BPY with a similar structure, these viologen-based porous organic polymers bear high charge density, phenyl ring and nitrogenous affinity sites, which endow them with excellent iodine vapor uptake capacity (4860 mg g−1 for POP-V-VI and 4200 mg g−1 for POP-V-BPY) and remarkably high adsorption capacity for pyridine (4470 mg g−1 for POP-V-VI and 8880 mg g−1 for POP-V-BPY) and other aliphatic amines. POP-V-VI and POP-V-BPY could be efficiently recycled and reused three times without significant loss of iodine vapor uptake. All these results demonstrate that POP-V-VI and POP-V-BPY are promising adsorbents for practical applications in portable devices such as gas masks.

Effects of Phase State and Phase Separation on Dimethylamine Uptake of Ammonium Sulfate and Ammonium Sulfate–Sucrose Mixed Particles

Unexpectedly high amounts of aminium salts have been detected in ambient aerosol particles, prompting investigations into their role in new particle formation and nanoparticle growth. Amine uptake ...

Gas phase amine depletion created by aerosol formation and growth

Aerosols are systems of droplets or wet particles suspended in gases. In post combustion CO2 absorption systems aerosols can be formed by spontaneous phase transitions in supersaturated gas phases or by droplets or particles entering the absorber with the gas to be treated. Micron and sub-micron mist droplets and fog formed in these processes cannot be removed by conventional demisting devices and because amine may be absorbed in the droplets this may increase dramatically the amine emissions from absorption columns as reported previously (Khakharia et al., 2015; Schaber et al., 2002). Thus, it is important to understand the mechanisms governing droplet growth and amine uptake through absorber as well as the effect large numbers of aerosol droplets can have on the bulk gas phase composition.A model developed and implemented in Matlab, predicts how the gas phase composition and temperature change along the absorber taking into account mass and heat transfer to and from both the bulk liquid and the droplet phase. The objective of this work, compared to earlier work, Majeed et al. (2017), is to study the possible effect of gas phase component depletion on the droplet growth and droplet internal variable profiles and how this varies with initial droplet size and composition, droplet number concentration and amine volatility.For MEA, as a relatively volatile solvent it is seen that gas phase depletion already takes place at number concentrations above 105 droplets/cm3 with an initial droplet radius of 1.5μ and 5M MEA initial concentration. For initial droplet radius 0.15μ and 0.0001M MEA initial concentration, which may be a more realistic case, hardly any depletion effect is seen up to 107 droplets/cm3. With change in amine volatility it is seen that the gas phase depletion effect is significantly stronger in the case of low volatility than for MEA at high droplet number concentrations. It is found that gas phase amine depletion has a strong effect on droplet growth.

C1-C2 alkyl aminiums in urban aerosols: Insights from ambient and fuel combustion emission measurements in the Yangtze River Delta region of China

We measured low molar-mass alkyl aminiums (methylaminium, dimethylaminium, ethylaminium and diethylaminium) in urban aerosols in the Yangtze River Delta region of eastern China in August 2014 and from November 2015 to May 2016. After examining artifact formation on sample filters, methylaminium, dimethylaminium and ethylaminium concentrations were quantified. The three C1-C2 aminiums exhibited a unimodal size distribution that maximized between 0.56 and 1.0 μm. Their concentrations in PM2.5 were 5.7 ± 3.2 ng m−3, 7.9 ± 5.4 ng m−3 and 20.3 ± 16.6 ng m−3, respectively, with higher concentrations during the daytime and in warm seasons. On new particle growth days, amine uptake to particles larger than 56 nm was barely enhanced. The molar ratios of individual aminium/NH4+ in PM2.5 were on the order of 10−4 and 10−3. Aminiums were thus far less to out-compete ammonium (NH4+) in neutralizing acidic species in particle sizes down to 56 nm. Abundant nitrate (NO3−/SO42− molar ratio = ∼3) and its correlation to methylaminium and ethylaminium implied that nitrate might be more important aminium salt than sulfate in urban aerosols of this area. Direct measurement of particle-phase amine emission from coal and biomass burning showed that coal burning is an important atmospheric amine source, considering coal burning is top-ranked particulate matter source in China.

Role of oleic acid coating in the heterogeneous uptake of dimethylamine by ammonium sulfate particles

ABSTRACTReactive uptake by ammonium (NH4+) salts is one of the major pathways for the gas-to-particle partitioning of alkyl amines. Recent studies using particles of individual ammonium salts and mixtures with hydrophilic organics have revealed that the degree of amine uptake depends on the phase state of ammonium salts, the particulate water contents and particle viscosity. The role of hydrophobic organic compounds, another important category of particulate organics commonly detected in the ambient atmosphere, in amine uptake remains unknown. Here we report the uptake of dimethylamine (DMA) by ammonium sulfate (AS) particles coated with fresh or ozone-aged bulk oleic acid (OA) at 60%, 30%, and <5% relative humidities (RHs) using an electrodynamic balance coupled with Raman spectroscopy. OA and DMA were selected to represent hydrophobic organics and alkyl amines, respectively. Over 74% of the original NH4+ ions were displaced due to DMA uptake, except those conditioned at <5% RH. On the other hand, the fr...

Perivascular Adipose Tissue's Impact on Norepinephrine-Induced Contraction of Mesenteric Resistance Arteries.

Background: Perivascular adipose tissue (PVAT) can decrease vascular contraction to NE. We tested the hypothesis that metabolism and/or uptake of vasoactive amines by mesenteric PVAT (MPVAT) could affect NE-induced contraction of the mesenteric resistance arteries.Methods: Mesenteric resistance vessels (MRV) and MPVAT from male Sprague-Dawley rats were used. RT-PCR and Western blots were performed to detect amine metabolizing enzymes. The Amplex® Red Assay was used to quantify oxidase activity by detecting the oxidase reaction product H2O2 and the contribution of PVAT on the mesenteric arteries' contraction to NE was measured by myography.Results: Semicarbazide sensitive amine oxidase (SSAO) and monoamine oxidase A (MAO-A) were detected in MRV and MPVAT by Western blot. Addition of the amine oxidase substrates tyramine or benzylamine (1 mM) resulted in higher amine oxidase activity in the MRV, MPVAT, MPVAT's adipocyte fraction (AF), and the stromal vascular fraction (SVF). Inhibiting SSAO with semicarbazide (1 mM) decreased amine oxidase activity in the MPVAT and AF. Benzylamine-driven, but not tyramine-driven, oxidase activity in the MRV was reduced by semicarbazide. By contrast, no reduction in oxidase activity in all sample types was observed with use of the monoamine oxidase inhibitors clorgyline (1 μM) or pargyline (1 μM). Inhibition of MAO-A/B or SSAO individually did not alter contraction to NE. However, inhibition of both MAO and SSAO increased the potency of NE at mesenteric arteries with PVAT. Addition of MAO and SSAO inhibitors along with the H2O2 scavenger catalase reduced PVAT's anti-contractile effect to NE. Inhibition of the norepinephrine transporter (NET) with nisoxetine also reduced PVAT's anti-contractile effect to NE.Conclusions: PVAT's uptake and metabolism of NE may contribute to the anti-contractile effect of PVAT. MPVAT and adipocytes within MPVAT are a source of SSAO.

Knudsen cell studies of the uptake of gaseous ammonia and amines onto C3-C7 solid dicarboxylic acids.

While atmospheric particles affect health, visibility and climate, the details governing their formation and growth are poorly understood on a molecular level. A simple model system for understanding the interactions between the gas and particle phases is the reaction of bases with acids, both of which are common constituents of atmospheric particles. In the present study, uptake coefficients for the reactions of gas phase ammonia, methylamine, ethylamine, dimethylamine and trimethylamine with a series of solid dicarboxylic acids (diacids) were measured at 296 ± 1 K using a Knudsen cell interfaced to a quadrupole mass spectrometer. The uptake coefficients (γ) for a given amine follow an odd-even trend in carbon number of the diacid, and are larger for the odd carbon diacids. Values range from γ = 0.4 for ethylamine on malonic acid (C3) to less than ∼10-6 for ammonia and all amines on adipic (C6) and pimelic (C7) acids. Basicity or structure of the amines/ammonia alone do not explain the effect of the base on uptake. The crystal structures of the diacids also play a key role, which is especially evident for malonic acid (C3). Evaporation of aqueous mixtures of amines/ammonia with odd carbon diacids show the formation of ionic liquids (ILs) or in some cases, metastable ILs that revert back to a stable solid salt upon complete evaporation of water. The trends with amine and diacid structure provide insight into the mechanisms of uptake and molecular interactions that control it, including the formation of ionic liquid layers in some cases. The diversity in the kinetics and mechanisms involved in this relatively simple model system illustrate the challenges in accurately representing such processes in atmospheric models.

Reactive Uptake of Dimethylamine by Ammonium Sulfate and Ammonium Sulfate-Sucrose Mixed Particles.

Short-chain alkyl amines can undergo gas-to-particle partitioning via reactive uptake by ammonium salts, whose phases have been thought to largely influence the extent of amine uptake. Previous studies mainly focused on particles of single ammonium salt at either dry or wet conditions without any addition of organic compounds. Here we report the uptake of dimethylamine (DMA) by ammonium sulfate (AS) and AS-sucrose mixed particles at different relative humidities (RHs) using an electrodynamic balance coupled with in situ Raman spectroscopy. DMA is selected as a representative of short-chain alkyl amines, and sucrose is used as a surrogate of viscous and hydrophilic organics. Effective DMA uptake was observed for most cases, except for the water-limiting scenario at <5% RH and the formation of an ultraviscous sucrose coating at 10% RH and below. DMA uptake coefficients (γ) were estimated using the particle mass measurements during DMA uptake. Addition of sucrose can increase γ by absorbing water or inhibiting AS crystallization and decrease γ by elevating the particle viscosity and forming a coating layer. DMA uptake can be facilitated for crystalline AS or retarded for aqueous AS with hydrophilic viscous organics (e.g., secondary organic material formed via the oxidation of biogenic volatile organic compounds) present in aerosol particles.

Effects of amines on particle growth observed in new particle formation events

AbstractParticle size distributions in the range of 0.01–10 µm were measured in urban Shanghai in the summer of 2013 using a Wide‐range Particle Spectrometer (WPS). Size‐segregated aerosol samples were collected concurrently using a Micro‐Orifice Uniform Deposit Impactor (MOUDI), which aided our in‐depth understanding of the new particle formation (NPF) mechanism in the polluted Yangtze River Delta area. During the observations, 16 NPF events occurred at high temperatures (~34.7°C) on clear and sunny days. In the ammonium‐poor PM1.0 (particulate matter less than 1.0 µm), sulfate and ammonium accounted for 92% of the total water‐soluble inorganic species. Six aminiums were detected in these MOUDI samples, among which the group of diethylaminium and trimethylaminium (DEAH+ + TMAH+) was the most abundant. The very high level of aminiums (average concentration up to 86.4 ng m−3 in PM1.8), together with highly acidic aerosols, provided insight into the frequent NPF events. The high mass ratio of total aminiums to NH4+ (&gt;0.2 for PM0.056) further highlighted the important role of amines in promoting NPF. The concentration of DEAH+ + TMAH+ in new particles below 180 nm was strongly correlated with aerosol phase acidity, indicating that acid‐base reactions dominated the aminium formation in NPF events. The unexpected enhancement of DEAH+ + TMAH+ on a nonevent day was attributed to the transportation of an SO2 plume. Our results reveal that the heterogeneous uptake of amines is dominated by the acid‐base reaction mechanism, which can effectively contribute to particle growth in NPF events.

The cytotoxicity of the α1-adrenoceptor antagonist prazosin is linked to an endocytotic mechanism equivalent to transport-P.

Since the α1-adrenergic antagonist prazosin (PRZ) was introduced into medicine as a treatment for hypertension and benign prostate hyperplasia, several studies have shown that PRZ induces apoptosis in various cell types and interferes with endocytotic trafficking. Because PRZ is also able to induce apoptosis in malignant cells, its cytotoxicity is a focus of interest in cancer research. Besides inducing apoptosis, PRZ was shown to serve as a substrate for an amine uptake mechanism originally discovered in neurones called transport-P. In line with our hypothesis that transport-P is an endocytotic mechanism also present in non-neuronal tissue and linked to the cytotoxicity of PRZ, we tested the uptake of QAPB, a fluorescent derivative of PRZ, in cancer cell lines in the presence of inhibitors of transport-P and endocytosis. Early endosomes and lysosomes were visualised by expression of RAB5-RFP and LAMP1-RFP, respectively; growth and viability of cells in the presence of PRZ and uptake inhibitors were also tested. Cancer cells showed co-localisation of QAPB with RAB5 and LAMP1 positive vesicles as well as tubulation of lysosomes. The uptake of QAPB was sensitive to transport-P inhibitors bafilomycin A1 (inhibits v-ATPase) and the antidepressant desipramine. Endocytosis inhibitors pitstop® 2 (general inhibitor of endocytosis), dynasore (dynamin inhibitor) and methyl-β-cyclodextrin (cholesterol chelator) inhibited the uptake of QAPB. Bafilomycin A1 and methyl-β-cyclodextrin but not desipramine were able to preserve growth and viability of cells in the presence of PRZ. In summary, we confirmed the hypothesis that the cellular uptake of QAPB/PRZ represents an endocytotic mechanism equivalent to transport-P. Endocytosis of QAPB/PRZ depends on a proton gradient, dynamin and cholesterol, and results in reorganisation of the LAMP1 positive endolysosomal system. Finally, the link seen between the cellular uptake of PRZ and cell death implies a still unknown pro-apoptotic membrane protein with affinity towards PRZ.

Phase considerations in the gas/particle partitioning of organic amines in the atmosphere

Abstract Amines in the atmosphere are of interest because of their likely role in new particle formation, and because of anthropogenic emissions of amines at post-combustion carbon capture (PCCC) facilities. A conceptual framework for considering the partitioning of a monobasic amine (Am = unprotonated, “free-base form”) from the gas phase to atmospheric particulate matter (PM) is presented for cases when the PM may be composed of multiple liquid phases. Three types of liquid phases are considered as being individually or simultaneously possible for absorptive uptake of atmospheric amines: w) a mostly water phase; α) a mostly (by mass) organic phase that has at least some polarity (e.g., predominantly secondary organic aerosol (SOA), may contain significant water on a mole fraction basis); and β) a mostly organic phase that is less polar than an α phase (e.g., predominantly primary organic aerosol (POA), containing little water). That one or more salts may contain the aminium ion AmH+ (formed by protonation of Am) is subject to the fact that the trace levels of individual amines in the atmosphere make formation of a pure solid such as AmHHSO4(s) exceedingly unlikely: when solid salts of AmH+ are indeed present, by far the most likely form is as a solid solution, e.g., ( NH 4 + ) 1 − y ( AmH + ) y HSO 4 ( s ) − where y K p,tot ( m 3 μg − 1 ) = c p,tot / c g = ∑ θ f θ K p,fb θ / α fb θ . The quantity cp,tot (μg μg−1) is the total Am concentration (Am + AmH+) in the PM as summed over all phases using the index θ (= w, α, β); cg is the gas-phase concentration of Am; f θ is the mass fraction of the total PM that is the θ phase; K p,fb θ is the gas/particle partitioning constant for the free-base (Am) form to the θ phase; and 0 α fb θ f w K p,fb w / α fb w . However, unless the PM contains little or no organic-phase material, the α and/or β terms are likely to also be relevant. The Am form of a low MW amine will in general have reasonable affinities for both α and β type phases, so in general K p,fb w , K p,fb α , and K p,fb β will all be roughly similar in magnitude. And, with significant water uptake into an α phase certain to occur at moderate to high RH values, solvation of ions will often be possible in an α phase. This will assist protonation of Am to AmH+ (as is known to occur for nicotine in tobacco smoke PM). The overall result is that to a first approximation, α fb w and α fb α can be similar in magnitude, making K p,fb α / α fb α likely to be generally comparable to K p,fb w / α fb w . In a β phase, ion solvation will not be as good, so that for acidic aerosol α fb β will generally be closer to one than the other two α fb values, making K p,fb β / α fb β smaller than both K p,fb w / α fb w and K p,fb α / α fb α . Overall, modeling of amine behavior in the atmosphere should include consideration of partitioning into organic PM. Unfortunately, this will be more difficult than water-phase only modeling because prediction of α fb values in multiphase PM will be greatly complicated by the needs to: 1) have estimated values of acidity constants in mostly organic phases of variable composition; and 2) allow distribution of chemicals over multiple liquid phases.

Prediction and validation of enzyme and transporter off-targets for metformin.

Metformin, an established first-line treatment for patients with type 2 diabetes, has been associated with gastrointestinal (GI) adverse effects that limit its use. Histamine and serotonin have potent effects on the GI tract. The effects of metformin on histamine and serotonin uptake were evaluated in cell lines overexpressing several amine transporters (OCT1, OCT3 and SERT). Metformin inhibited histamine and serotonin uptake by OCT1, OCT3 and SERT in a dose-dependent manner, with OCT1-mediated amine uptake being most potently inhibited (IC50 = 1.5 mM). A chemoinformatics-based method known as Similarity Ensemble Approach predicted diamine oxidase (DAO) as an additional intestinal target of metformin, with an E-value of 7.4 × 10(-5). Inhibition of DAO was experimentally validated using a spectrophotometric assay with putrescine as the substrate. The Ki of metformin for DAO was measured to be 8.6 ± 3.1 mM. In this study, we found that metformin inhibited intestinal amine transporters and DAO at concentrations that may be achieved in the intestine after therapeutic doses. Further studies are warranted to determine the relevance of these interactions to the adverse effects of metformin on the gastrointestinal tract.

Indanes--Properties, Preparation, and Presence in Ligands for G Protein Coupled Receptors.

The indane (2,3-dihydro-1H-indene) ring system is an attractive scaffold for biologically active compounds due to the combination of aromatic and aliphatic properties fused together in one rigid system. This bicyclic structure provides a wide range of possibilities to incorporate specific substituents in different directionalities, thus being an attractive scaffold for medicinal chemists. Notably, many indane-based compounds are being used in the clinic to treat various diseases, such as indinavir, an HIV-1 protease inhibitor; indantadol, a potent Monoamine Oxidase (MAO)-inhibitor; the amine uptake inhibitor indatraline; and the ultra-long-acting β-adrenoceptor agonist indacaterol. Given the diversity of targets these drugs act on, one could argue that the indane ring system is a privileged substructure. In the present review, the synthetic and medicinal chemistry of the indane ring system is described. In more detail, it contains a comprehensive overview of compounds bearing the indane substructure with G protein coupled receptor (GPCR) activity, with particular emphasis on their structure-activity relationships (SAR).

Surfactant protein A (SP-A) inhibits agglomeration and macrophage uptake of toxic amine modified nanoparticles

The lung provides the main route for nanomaterial exposure. Surfactant protein A (SP-A) is an important respiratory innate immune molecule with the ability to bind or opsonise pathogens to enhance phagocytic removal from the airways. We hypothesised that SP-A, like surfactant protein D, may interact with inhaled nanoparticulates, and that this interaction will be affected by nanoparticle (NP) surface characteristics. In this study, we characterise the interaction of SP-A with unmodified (U-PS) and amine-modified (A-PS) polystyrene particles of varying size and zeta potential using dynamic light scatter analysis. SP-A associated with both 100 nm U-PS and A-PS in a calcium-independent manner. SP-A induced significant calcium-dependent agglomeration of 100 nm U-PS NPs but resulted in calcium-independent inhibition of A-PS self agglomeration. SP-A enhanced uptake of 100 nm U-PS into macrophage-like RAW264.7 cells in a dose-dependent manner but in contrast inhibited A-PS uptake. Reduced association of A-PS particles in RAW264.7 cells following pre-incubation of SP-A was also observed with coherent anti-Stokes Raman spectroscopy. Consistent with these findings, alveolar macrophages (AMs) from SP-A−/− mice were more efficient at uptake of 100 nm A-PS compared with wild type C57Bl/6 macrophages. No difference in uptake was observed with 500 nm U-PS or A-PS particles. Pre-incubation with SP-A resulted in a significant decrease in uptake of 100 nm A-PS in macrophages isolated from both groups of mice. In contrast, increased uptake by AMs of U-PS was observed after pre-incubation with SP-A. Thus we have demonstrated that SP-A promotes uptake of non-toxic U-PS particles but inhibits the clearance of potentially toxic A-PS particles by blocking uptake into macrophages.

Correlations between Blood–Brain Barrier Disruption and Neuroinflammation in an Experimental Model of Penetrating Ballistic-Like Brain Injury

Abstract Blood-brain barrier (BBB) disruption is a pathological hallmark of severe traumatic brain injury (TBI) and is associated with neuroinflammatory events contributing to brain edema and cell death. The goal of this study was to elucidate the profile of BBB disruption after penetrating ballistic-like brain injury (PBBI) in conjunction with changes in neuroinflammatory markers. Brain uptake of biotin-dextran amine (BDA; 3 kDa) and horseradish peroxidase (HRP; 44 kDa) was evaluated in rats at 4 h, 24 h, 48 h, 72 h, and 7 days post-PBBI and compared with the histopathologic and molecular profiles for inflammatory markers. BDA and HRP both displayed a uniphasic profile of extravasation, greatest at 24 h post-injury and which remained evident out to 48 h for HRP and 7 days for BDA. This profile was most closely associated with markers for adhesion (mRNA for intercellular adhesion molecule-1) and infiltration of peripheral granulocytes (mRNA for matrix metalloproteinase-9 [MMP-9] and myeloperoxidase staining). Improvement of BBB dysfunction coincided with increased expression of markers implicated in tissue remodeling and repair. The results of this study reveal a uniphasic and gradient opening of the BBB after PBBI and suggest MMP-9 and resident inflammatory cell activation as candidates for future neurotherapeutic intervention after PBBI.

Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.