Where the linearized Poisson-Boltzmann cell model fails: (I) spurious phase separation in charged colloidal suspensions

We perform a linearization of the Poisson-Boltzmann (PB) density functional for spherical Wigner-Seitz cells that yields Debye-H\"uckel-like equations agreeing asymptotically with the PB results in the weak-coupling (high-temperature) limit. Both the canonical (fixed number of microions) as well as the semi-grand-canonical (in contact with an infinite salt reservoir) cases are considered and discussed in a unified linearized framework. In the canonical case, for sufficiently large colloidal charges the linearized theory predicts the occurrence of a thermodynamical instability with an associated phase separation of the homogeneous suspension into dilute (gas) and dense (liquid) phases. In the semi-grand-canonical case it is predicted that the isothermal compressibility and the osmotic-pressure difference between the colloidal suspension and the salt reservoir become negative in the low-temperature, high-surface charge or infinite-dilution (of polyions) limits. As already pointed out in the literature for the latter case, these features are in disagreement with the exact nonlinear PB solution inside a Wigner-Seitz cell and are thus artifacts of the linearization. By using explicitly gauge-invariant forms of the electrostatic potential we show that these artifacts, although thermodynamically consistent with quadratic expansions of the nonlinear functional and osmotic pressure, may be traced back to the non-fulfillment of the underlying assumptions of the linearization.Comment: 32 pages, 3 PostScript figures, submitted to J. Chem. Phy

The ABCB1 transporter gene and antidepressant response

P-glycoprotein, encoded by the ABCB1 gene, may modulate the brain concentration of several antidepressants. Functional genetic variation is thought to exist in this gene, and here we review several studies that have attempted to associate this variation with clinical response to antidepressant treatment

Spatial and temporal distribution of atmospheric aerosols in the lowermost troposphere over the Amazonian tropical rainforest

International audienceWe present measurements of aerosol physico-chemical properties below 5 km altitude over the tropical rain forest and the marine boundary layer (MBL) obtained during the LBA-CLAIRE 1998 project. The MBL aerosol size distribution some 50-100km of the coast of French Guyana and Suriname showed a bi-modal shape typical of aged and cloud processed aerosol. The average particle number density in the MBL was 383cm-3. The daytime mixed layer height over the rain forest for undisturbed conditions was estimated to be between 1200-1500m. During the morning hours the height of the mixed layer increased by 144-180mh-1. The median daytime aerosol number density in the mixed layer increased from 450cm-3 in the morning to almost 800cm-3 in the late afternoon. The evolution of the aerosol size distribution in the daytime mixed layer over the rain forest showed two distinct patterns. Between dawn and midday, the Aitken mode particle concentrations increased, whereas later during the day, a sharp increase of the accumulation mode aerosol number densities was observed, resulting in a doubling of the morning accumulation mode concentrations from 150cm-3 to 300cm-3. Potential sources of the Aitken mode particles are discussed here including the rapid growth of ultrafine aerosol particles formed aloft and subsequently entrained into the mixed layer, as well as the contribution of emissions from the tropical vegetation to Aitken mode number densities. The observed increase of the accumulation mode aerosol number densities is attributed to the combined effect of: the direct emissions of primary biogenic particles from the rain forest and aerosol in-cloud processing by shallow convective clouds. Based on the similarities among the number densities, the size distributions and the composition of the aerosol in the MBL and the nocturnal residual layer we propose that the air originating in the MBL is transported above the nocturnal mixed layer up to 300-400km inland over the rain forest by night without significant processing

Single particle analysis of the accumulation mode aerosol over the northeast Amazonian tropical rain forest, Surinam, South America

International audienceSingle particle analysis of aerosols particles larger than 0.2 ?m diameter was performed on 24 samples collected over Surinam tropical rain forest and in the adjacent marine boundary layer (MBL) during the LBA-CLAIRE 98 campaign in March 1998. Elemental composition and morphology of 2308 particles was determined using SEM-EDX. The aerosol particles were divided into seven groups according to their chemical composition: organic particles, mineral dust, aged mineral dust, sea salt, aged sea salt, Ca-rich, and biogenic aerosol. However the organic material in aerosol particles cannot be identified directly by SEM-EDX, we present indirect method of detection of organic material using this technique. Samples were further divided with respect to the distinct atmospheric layers present in the tropical troposphere including MBL, continental mixed layer, cloud convective layer, free troposphere and region of deep convection outflow. The organic and mineral dust particles are two major groups observed over the rainforest. In the MBL also sea salt particles represented a large fraction between 15 and 27%. The organic particles control much of the chemical characteristic of the aerosol in the continental tropical troposphere. Their abundance ranged from less than 20% in the MBL to more than 90% in the free troposphere between 4.5- and 12.6-km altitude. During the transport of the air masses from the MBL over the rain forest, fraction of organic aerosol particles more than doubled, reaching 40?60% in the continental boundary layer. This increase was attributed to direct emissions of biogenic aerosols from the tropical vegetation. The high fraction of the organic accumulation mode particles in the upper tropical troposphere could be a good indicator for the air masses originated over the tropical rain forest

Many-body interactions and melting of colloidal crystals

We study the melting behavior of charged colloidal crystals, using a simulation technique that combines a continuous mean-field Poisson-Boltzmann description for the microscopic electrolyte ions with a Brownian-dynamics simulation for the mesoscopic colloids. This technique ensures that many-body interactions between the colloids are fully taken into account, and thus allows us to investigate how many-body interactions affect the solid-liquid phase behavior of charged colloids. Using the Lindemann criterion, we determine the melting line in a phase-diagram spanned by the colloidal charge and the salt concentration. We compare our results to predictions based on the established description of colloidal suspensions in terms of pairwise additive Yukawa potentials, and find good agreement at high-salt, but not at low-salt concentration. Analyzing the effective pair-interaction between two colloids in a crystalline environment, we demonstrate that the difference in the melting behavior observed at low salt is due to many-body interactions

Dual role of benzophenone enables a fast and scalable C-4 selective alkylation of pyridines in flow

The efficient C-4 selective modification of pyridines is a major challenge for the synthetic community. Current strategies are plagued with at least one drawback regarding functional group-tolerant electronic activation of the heteroarene, mild generation of the required alkyl radicals, regioselectivity, safety and/or scalability. Herein, we describe a fast, safe and scalable flow process which allows preparation of said C-4 alkylated pyridines. The process involves a photochemical hydrogen atom transfer (HAT) event to generate the carbon-centered radicals needed to alkylate the C-2 blocked pyridine. In a two-step streamlined flow process, this light-mediated alkylation step is combined with a nearly instantaneous inline removal of the blocking group. Notably, cheap benzophenone plays a dual role in the pyridine alkylation mechanism by activating the hydrocarbon feedstock reagents via a HAT mechanism, and by acting as a benign, terminal oxidant. The key role of benzophenone in the operative reaction mechanism has also been revealed through a combination of experimental and computational studies

Oxygenated compounds in aged biomass burning plumes over the Eastern Mediterranean: evidence for strong secondary production of methanol and acetone

International audienceAirborne measurements of acetone, methanol, PAN, acetonitrile (by Proton Transfer Reaction Mass Spectrometry), and CO (by Tunable Diode Laser Absorption Spectroscopy) have been performed during the Mediterranean Intensive Oxidants Study (MINOS August 2001). We have identified ten biomass burning plumes from strongly elevated acetonitrile mixing ratios. The characteristic biomass burning signatures obtained from these plumes reveal secondary production of acetone and methanol, while CO photochemically declines in the plumes. Mean excess mixing ratios - normalized to CO - of 1.8%, 0.20%, 3.8%, and 0.65% for acetone, acetonitrile, methanol, and PAN, respectively, were found. By scaling to an assumed global annual source of 663-807Tg CO, biomass burning emissions of 25-31 and 29-35 Tg/yr for acetone and methanol are estimated, respectively. Our measurements suggest that the present biomass burning contributions of acetone and methanol are significantly underestimated due to the neglect of secondary formation within the plume. Median acetonitrile mixing ratios throughout the troposphere were around 150pmol/mol, in accord with current biomass burning inventories and an atmospheric lifetime of ~6 months