Effects of carbon surface chemistry and solution pH on the adsorption of binary aromatic solutes

Adsorption of p-cresol, nitrobenzene and p-nitrophenol on treated and untreated carbons is investigated systematically. The effects of carbon surface chemistry and solution pH are studied and discussed. All adsorption experiments were carried out in pH-controlled solutions to examine the adsorption properties of the adsorption systems where the solutes are in molecular as well as ionic forms. Using the homogeneous Langmuir equation, the single solute parameters are determined. These parameters are then used to predict the binary solute adsorption isotherms and gain further insights into the adsorption process. (C) 2002 Elsevier Science Ltd. All rights reserved.

Effects of potential models on the adsorption of ethane and ethylene on graphitized thermal carbon black. Study of two-dimensional critical temperature and isosteric heat versus loading

Adsorption of ethylene and ethane on graphitized thermal carbon black and in slit pores whose walls are composed of graphene layers is studied in detail to investigate the packing efficiency, the two-dimensional critical temperature, and the variation of the isosteric heat of adsorption with loading and temperature. Here we used a Monte Carlo simulation method with a grand canonical Monte Carlo ensemble. A number of two-center Lennard-Jones (LJ) potential models are investigated to study the impact of the choice of potential models in the description of adsorption behavior. We chose two 2C-LJ potential models in our investigation of the (i) UA-TraPPE-LJ model of Martin and Siepmann (J. Phys. Chem. B 1998,102, 25692577) for ethane and Wick et al. (J. Phys. Chem. B 2000,104, 8008-8016) for ethylene and (ii) AUA4-LJ model of Ungerer et al. (J. Chem. Phys. 2000,112, 5499-5510) for ethane and Bourasseau et al. (J. Chem. Phys. 2003, 118, 3020-3034) for ethylene. These models are used to study the adsorption of ethane and ethylene on graphitized thermal carbon black. It is found that the solid-fluid binary interaction parameter is a function of adsorbate and temperature, and the adsorption isotherms and heat of adsorption are well described by both the UA-TraPPE and AUA models, although the UA-TraPPE model performs slightly better. However, the local distributions predicted by these two models are slightly different. These two models are used to explore the two-dimensional condensation for the graphitized thermal carbon black, and these values are 110 K for ethylene and 120 K for ethane.

Site-directed mutagenesis and kinetic studies of the West Nile virus NS3 protease identify key enzyme-substrate interactions

The flavivirus West Nile virus (WNV) has spread rapidly throughout the world in recent years causing fever, meningitis, encephalitis, and fatalities. Because the viral protease NS2B/NS3 is essential for replication, it is attracting attention as a potential therapeutic target, although there are currently no antiviral inhibitors for any flavivirus. This paper focuses on elucidating interactions between a hexapeptide substrate (Ae-KPGLKR-p-nitroanilide) and residues at S1 and S2 in the active site of WNV protease by comparing the catalytic activities of selected mutant recombinant proteases in vitro. Homology modeling enabled the predictions of key mutations in VWNV NS3 protease at S1 (V115A/F, D129A/ E/N, S135A, Y150A/F, S160A, and S163A) and S2 (N152A) that might influence substrate recognition and catalytic efficiency. Key conclusions are that the substrate P1 Arg strongly interacts with S1 residues Asp-129, Tyr-150, and Ser-163 and, to a lesser extent, Ser-160, and P2 Lys makes an essential interaction with Asn-152 at S2. The inferred substrate-enzyme interactions provide a basis for rational protease inhibitor design and optimization. High sequence conservation within flavivirus proteases means that this study may also be relevant to design of protease inhibitors for other flavivirus proteases.

Addition of cue exposure to cognitive-behaviour therapy for alcohol misuse: a randomized trial with dysphoric drinkers

Aim To test whether addition of moderation-orientated cue exposure (CE) or CE after dysphoric mood induction ( emotional CE, ECE) improved outcomes above those from cognitive-behaviour therapy alone (CBT) in people who drank when dysphoric. Design Multi-site randomized controlled trial comparing CBT with CBT + CE and CBT + ECE. Setting Out-patient rooms in academic treatment units in Brisbane and Sydney, Australia. Participants People with alcohol misuse and problems controlling consumption when dysphoric (n = 163). Those with current major depressive episode were excluded. Intervention Eight weekly 75-minute sessions of individual treatment for alcohol problems were given to all participants, with CBT elements held constant across conditions. From session 2, CBT + CE participants resisted drinking while exposed to alcohol cues, with two priming doses of their preferred beverage being given in some sessions. After an initial CE session, CBT + ECE participants recalled negative experiences before undertaking CE, to provide exposure to emotional cues of personal relevance. Measurements Alcohol consumption, related problems, alcohol expectancies, self-efficacy and depression. Results Average improvements were highly significant across conditions, with acceptable maintenance of effects over 12 months. Both treatment retention and effects on alcohol consumption were progressively weaker in CBT + CE and CBT + ECE than in CBT alone. Changes in alcohol dependence and depression did not differ across conditions. Conclusions These data do not indicate that addition of clinic-based CE to standard CBT improves outcomes. A different approach to the management of craving may be required.

Effect of adsorption deformation on thermodynamic characteristics of a fluid in slit pores at sub-critical conditions

Solvation. pressure due to adsorption of fluids in porous materials is the cause of elastic deformation of an adsorbent, which is accessible to direct experimental measurements. Such a deformation contributes to the Helmholtz free energy of the whole adsorbent-adsorbate system due to accumulation of compression or tension energy by the solid. It means that in the general case the solid has to be considered as not solely a source of the external potential field for the fluid confined in the pore volume, but also as thermodynamically nonmert component of the solid-fluid system. We present analysis of nitrogen adsorption isotherms and heat of adsorption in slit graphitic pores accounting for the adsorption deformation by means of nonlocal density functional theory. (c) 2006 Elsevier Ltd. All rights reserved.

Influence of adsorbate interaction on transport in confined spaces

This article provides a review of the recent theory of transport in nanopores developed in the author's laboratory. In particular the influence of fluid-solid interactions on the transport coefficient is examined, showing that such interactions reduce the value of the coefficient by almost an order of magnitude in comparison to the Knudsen theory for non-interacting systems. The activation energy and potential energy barriers for diffusion in smooth pores with a one-dimensional potential energy profile are also discussed, indicating the inadequacy of the commonly used assumption of proportionality between the activation energy and heat of adsorption or the minimum pore potential energy. A further feature affected by fluid-solid interactions is the nature of the reflection of fluid molecules colliding with a pore wall surface, varying from being nearly specular - such as in carbon nanotubes - to nearly diffuse for amorphous solids. Diffuse reflection leads to momentum loss and reduced transport coefficients. However, fluid-solid interactions do not affect the transport coefficient in the single-file diffusion regime when the surface reflection is diffuse, and the transport coefficient in this case is largely independent of the adsorbed density.

Adsorption dynamics measured by permeation and batch adsorption methods

We have measured the adsorption equilibrium and kinetics of carbon dioxide on a commercially available activated carbon by two methods; permeation and batch adsorption. The two methods are compared and found to yield consistent results. All experiments are performed at low pressure (

The surface chemistry of nanocrystalline MgO catalysts for FAME production:an in situ XPS study of H2O, CH3OH and CH3OAc adsorption

An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O2 − sites to OH− and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C–H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects. Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

CO adsorption over Pd nanoparticles:a general framework for IR simulations on nanoparticles

CO vibrational spectra over catalytic nanoparticles under high coverages/pressures are discussed from a DFT perspective. Hybrid B3LYP and PBE DFT calculations of CO chemisorbed over Pd4 and Pd13 nanoclusters, and a 1.1 nm Pd38 nanoparticle, have been performed in order to simulate the corresponding coverage dependent infrared (IR) absorption spectra, and hence provide a quantitative foundation for the interpretation of experimental IR spectra of CO over Pd nanocatalysts. B3LYP simulated IR intensities are used to quantify site occupation numbers through comparison with experimental DRIFTS spectra, allowing an atomistic model of CO surface coverage to be created. DFT adsorption energetics for low CO coverage (θ → 0) suggest the CO binding strength follows the order hollow > bridge > linear, even for dispersion-corrected functionals for sub-nanometre Pd nanoclusters. For a Pd38 nanoparticle, hollow and bridge-bound are energetically similar (hollow ≈ bridge > atop). It is well known that this ordering has not been found at the high coverages used experimentally, wherein atop CO has a much higher population than observed over Pd(111), confirmed by our DRIFTS spectra for Pd nanoparticles supported on a KIT-6 silica, and hence site populations were calculated through a comparison of DFT and spectroscopic data. At high CO coverage (θ = 1), all three adsorbed CO species co-exist on Pd38, and their interdiffusion is thermally feasible at STP. Under such high surface coverages, DFT predicts that bridge-bound CO chains are thermodynamically stable and isoenergetic to an entirely hollow bound Pd/CO system. The Pd38 nanoparticle undergoes a linear (3.5%), isotropic expansion with increasing CO coverage, accompanied by 63 and 30 cm− 1 blue-shifts of hollow and linear bound CO respectively.

A case of bilateral perisylvian syndrome with reading disability

Bilateral Perisylvian Syndrome (BPS) often presents with epilepsy and significant behavioral impairments that can include mental retardation, dysarthria, delayed speech development, and delayed fine motor development (Graff-Radford et al., 1986 and Kuzniecky et al., 1993). While a small subset of BPS cases have been described as having relatively isolated language delays (Leventer et al., 2010), BPS is not expected in children with dyslexia. As part of a Medical University of South Carolina, IRB approved multi-site study involving retrospective and de-identified dyslexia data, we unexpectedly identified a 14.05 year old male with evidence of BPS whose father had been diagnosed with dyslexia and dysgraphia. This child had been recruited for a neuroimaging study on dyslexia from a school specializing in educating children with dyslexia. The T1-weighted MRI scan from this child demonstrated a highly unusual perisylvian sulcal/gyral patterning that is a defining feature of BPS (Fig. 1). BPS cases exhibit bilateral dysgenesis of the Sylvian fissure and surrounding gyri, which appears to occur because of a limited or absent arcuate fasciculus (Kilinc, Ekinci, Demirkol, & Agan, 2015). This BPS case also had a relatively enlarged atrium of the lateral ventricle that is consistent with the BPS anatomical presentation and reduction of parietal white matter (Graff-Radford et al., 1986, Kilinc et al., 2015 and Toldo et al., 2011).

Estimation of sea surface temperatures and salinity of ODP Site 177-1089 (Appendix A)

ODP Site 1089 is optimally located in order to monitor the occurrence of maxima in Agulhas heat and salt spillage from the Indian to the Atlantic Ocean. Radiolarian-based paleotemperature transfer functions allowed to reconstruct the climatic history for the last 450 kyr at this location. A warm sea surface temperature anomaly during Marine Isotope Stage (MIS) 10 was recognized and traced to other oceanic records along the surface branch of the global thermohaline (THC) circulation system, and is particularly marked at locations where a strong interaction between oceanic and atmospheric overturning cells and fronts occurs. This anomaly is absent in the Vostok ice core deuterium, and in oceanic records from the Antarctic Zone. However, it is present in the deuterium excess record from the Vostok ice core, interpreted as reflecting the temperature at the moisture source site for the snow precipitated at Vostok Station. As atmospheric models predict a subtropical Indian source for such moisture, this provides the necessary teleconnection between East Antarctica and ODP Site 1089, as the subtropical Indian is also the source area of the Agulhas Current, the main climate agent at our study location. The presence of the MIS 10 anomaly in the delta13C foraminiferal records from the same core supports its connection to oceanic mechanisms, linking stronger Agulhas spillover intensity to increased productivity in the study area. We suggest, in analogy to modern oceanographic observations, this to be a consequence of a shallow nutricline, induced by eddy mixing and baroclinic tide generation, which are in turn connected to the flow geometry, and intensity, of the Agulhas Current as it flows past the Agulhas Bank. We interpret the intensified inflow of Agulhas Current to the South Atlantic as responding to the switch between lower and higher amplitude in the insolation forcing in the Agulhas Current source area. This would result in higher SSTs in the Cape Basin during the glacial MIS 10, due to the release into the South Atlantic of the heat previously accumulating in the subtropical and equatorial Indian and Pacific Ocean. If our explanation for the MIS 10 anomaly in terms of an insolation variability switch is correct, we might expect that a future Agulhas SSST anomaly event will further delay the onset of next glacial age. In fact, the insolation forcing conditions for the Holocene (the current interglacial) are very similar to those present during MIS 11 (the interglacial preceding MIS 10), as both periods are characterized by a low insolation variability for the Agulhas Current source area. Natural climatic variability will force the Earth system in the same direction as the anthropogenic global warming trend, and will thus lead to even warmer than expected global temperatures in the near future.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

Calcareous nannofossils and C37 alkenones at ODP Site 162-982

During the late Pliocene (~3 to 2.5 Ma), oceanic records of opal and C37 alkenone accumulation from around the world show a secular shift towards lower values in the high latitudes and higher values in the low and mid latitudes. These shifts are broadly coincident with the intensification of northern hemisphere glaciation and are suggestive of changes in export productivity, with potential implications for Pliocene atmospheric carbon dioxide concentrations. The interpretation of a global latitudinal shift in productivity, however, requires testing because of the potential uncertainties associated with site to site comparisons of records that can be influenced by highly nonlinear processes associated with production, export, and preservation. Here, we assess the inferred Pliocene latitudinal productivity shift interpretation by presenting new records of C37 alkenone accumulation from Ocean Drilling Program (ODP) Site 982 in the North Atlantic and biotic assemblages (calcareous nannoplankton) from this site and ODP Site 846 in the eastern tropical Pacific. Our results corroborate the interpretation of C37 alkenone accumulation as a proxy for gross export productivity at these sites, indicating that large-scale productivity decreases at high latitudes and increases at tropical sites are recorded robustly. We conclude that the intensification of northern hemisphere glaciation during the late Pliocene was associated with a profound reorganisation of ocean biogeochemistry.

(Table 1) Sample descriptions, carbon contents, and lipid yields across the K/T boundary at DSDP Hole 93-605 and at Stevns Klint, Denmark

This reconnaissance study was undertaken to determine whether the mass extinctions and faunal successions that mark the Cretaceous/Tertiary (K/T) boundary left a discernible molecular fossil record in the sediments of this period. Lipid signatures of sediments taken from above and below the K/T boundary were compared in core and outcrop samples taken from two locations: the U.S. east coast continental margin (western Atlantic Ocean, DSDP Site 605) and Stevns Klint, Denmark. Four calcareous sediments taken from above and below the K/T boundary in DSDP Hole 605, Section 605-66-1, revealed changing lipid signatures between above and below that are characterized by a large component of unresolved naphthenic hydrocarbons and a homologous series of n-alkanes ranging from Ci6 to C33. These lipid signatures are attributed to an influx of a terrestrial higher plant component and to bacterial reworking of the sediments under partially anoxic depositional and/or diagenetic conditions. The outcrop samples from Stevns Klint had extremely low concentrations of indigenous lipids. The fish clay at the K/T boundary contained traces of microbial hydrocarbons and fatty acids, whereas the carbonates above and below had only microbial fatty acids and additional terrestrial resin acids. The data from both sites indicate a perturbation in the deposition of lipid compound classes across the K/T boundary.

Annotated record of the detailed examination of Mn deposits from DSDP Site, Leg 4 (Cores 4-27-1 and 4-27A-1)

The northern margin of the Demerara Abyssal Plain is bordered by a low ESE-WNW trending rise known as the Barracuda Ridge. North of South America, the eastern margin of the Demerara Abyssal Plain is formed by the Barbados Ridge. An extensive sedimentary section of the Barbados Ridge is exposed on the island of Barbados and consists of a series of radiolarian to planktonic foraminiferal and calcareous nannofossil biogenic sediments interlayered with ash beds. To determine the nature of the sediments and "basement," Site 27 was selected on the northern margin of the Demerara Abyssal Plain, south of the Barracuda Ridge.