Self assembly of a model amphiphilic phenylalanine peptide/polyethylene glycol block copolymer in aqueous solution

There has been great interest recently in peptide amphiphiles and block copolymers containing biomimetic peptide sequences due to applications in bionanotechnology. We investigate the self-assembly of the peptide-PEG amphiphile FFFF-PEG5000 containing the hydrophobic sequence of four phenylalanine residues conjugated to PEG of molar mass 5000. This serves as a simple model peptide amphiphile. At very low concentration, association of hydrophobic aromatic phenylalanine residues occurs, as revealed by circular dichroism and UV/vis fluorescence experiments. A critical aggregation concentration associated with the formation of hydrophobic domains is determined through pyrene fluorescence assays. At higher concentration, defined beta-sheets develop as revealed by FTIR spectroscopy and X-ray diffraction. Transmission electron microscopy reveals self-assembled straight fibril structures. These are much shorter than those observed for amyloid peptides, the finite length may be set by the end cap energy due to the hydrophobicity of phenylalanine. The combination of these techniques points to different aggregation processes depending on concentration. Hydrophobic association into irregular aggregates occurs at low concentration, well-developed beta-sheets only developing at higher concentration. Drying of FFFF-PEG5000 solutions leads to crystallization of PEG, as confirmed by polarized optical microscopy (POM), FTIR and X-ray diffraction (XRD). PEG crystallization does not disrupt local beta-sheet structure (as indicated by FTIR and XRD). However on longer lengthscales the beta-sheet fibrillar structure is perturbed because spheruilites from PEG crystallization are observed by POM. (C) 2009 Elsevier B.V. All rights reserved.

New bis(triazinyl) pyridines for selective extraction of americium(III)

New hydrophobic, tridentate nitrogen heterocyclic reagents (BATPs) such as 2,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[1,2,4]triazin-3-yl) pyridine (1) and 2,6-bis(9,9,10,10-tetramethyl-9,10-dihydro-1,2,4-triaza-anthrane-3-yl) pyridine (2) have been studied. I is resistant to hydrolysis in 3 M nitric acid, whereas 2 is resistant to both acid hydrolysis and radiolysis. The molecules are able to give significantly enhanced separations of americium(III) from an excess of europium(III) in nitric acid. Typically, for 1 D-Am = 500 and SFAm,/Eu = 5000 compared with D-Am = 30 and SFAm /Eu = 400 with the reference molecule 2,6-bis(isopropyl[1,2,4]triazin-3-yl) pyridine (7). In order to increase the stability of 1 and 2, the labile alpha-benzylic hydrogens that are present in 7 have been replaced by alkyl groups. Three molecules of 1 are able to enclose completely the coordination sphere of the M(III) in the crystal structure of [Y(1)(3)][Y(NO3)(5)]center dot NO3 center dot 2.5H(2)O.

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

Gene transcription in Daphnia magna: effects of acute exposure to a carbamate insecticide and an acetanilide herbicide.

Daphnia magna is a key invertebrate in the freshwater environment and is used widely as a model in ecotoxicological measurements and risk assessment. Understanding the genomic responses of D. magna to chemical challenges will be of value to regulatory authorities worldwide. Here we exposed D. magna to the insecticide methomyl and the herbicide propanil to compare phenotypic effects with changes in mRNA expression levels. Both pesticides are found in drainage ditches and surface water bodies standing adjacent to crops. Methomyl, a carbamate insecticide widely used in agriculture, inhibits acetylcholinesterase, a key enzyme in nerve transmission. Propanil, an acetanilide herbicide, is used to control grass and broad-leaf weeds. The phenotypic effects of single doses of each chemical were evaluated using a standard immobilisation assay. Immobilisation was linked to global mRNA expression levels using the previously estimated 48h-EC(1)s, followed by hybridization to a cDNA microarray with more than 13,000 redundant cDNA clones representing >5000 unique genes. Following exposure to methomyl and propanil, differential expression was found for 624 and 551 cDNAs, respectively (one-way ANOVA with Bonferroni correction, P

Controls of carbon dioxide concentrations and fluxes above central London

Eddy-covariance measurements of carbon dioxide fluxes were taken semi-continuously between October 2006 and May 2008 at 190 m height in central London (UK) to quantify emissions and study their controls. Inner London, with a population of 8.2 million (~5000 inhabitants per km2) is heavily built up with 8% vegetation cover within the central boroughs. CO2 emissions were found to be mainly controlled by fossil fuel combustion (e.g. traffic, commercial and domestic heating). The measurement period allowed investigation of both diurnal patterns and seasonal trends. Diurnal averages of CO2 fluxes were found to be highly correlated to traffic. However changes in heating-related natural gas consumption and, to a lesser extent, photosynthetic activity that controlled the seasonal variability. Despite measurements being taken at ca. 22 times the mean building height, coupling with street level was adequate, especially during daytime. Night-time saw a higher occurrence of stable or neutral stratification, especially in autumn and winter, which resulted in data loss in post-processing. No significant difference was found between the annual estimate of net exchange of CO2 for the expected measurement footprint and the values derived from the National Atmospheric Emissions Inventory (NAEI), with daytime fluxes differing by only 3%. This agreement with NAEI data also supported the use of the simple flux footprint model which was applied to the London site; this also suggests that individual roughness elements did not significantly affect the measurements due to the large ratio of measurement height to mean building height.

The impact of the state of the troposphere on the response to stratospheric heating in a simplified GCM

Previous studies have made use of simplified general circulation models (sGCMs) to investigate the atmospheric response to various forcings. In particular, several studies have investigated the tropospheric response to changes in stratospheric temperature. This is potentially relevant for many climate forcings. Here the impact of changing the tropospheric climatology on the modeled response to perturbations in stratospheric temperature is investigated by the introduction of topography into the model and altering the tropospheric jet structure. The results highlight the need for very long integrations so as to determine accurately the magnitude of response. It is found that introducing topography into the model and thus removing the zonally symmetric nature of the model’s boundary conditions reduces the magnitude of response to stratospheric heating. However, this reduction is of comparable size to the variability in the magnitude of response between different ensemble members of the same 5000-day experiment. Investigations into the impact of varying tropospheric jet structure reveal a trend with lower-latitude/narrower jets having a much larger magnitude response to stratospheric heating than higher-latitude/wider jets. The jet structures that respond more strongly to stratospheric heating also exhibit longer time scale variability in their control run simulations, consistent with the idea that a feedback between the eddies and the mean flow is both responsible for the persistence of the control run variability and important in producing the tropospheric response to stratospheric temperature perturbations.

Built environment education and research in West Africa

Built environment programmes in West African universities; and research contributions from West Africa in six leading international journals and proceedings of the WABER conference are explored. At least 20 universities in the region offer degree programmes in Architecture (86% out of 23 universities); Building (57%); Civil Engineering (67%); Estate Management (52%); Quantity Surveying (52%); Surveying and Geoinformatics (55%); Urban and Regional Planning (67%). The lecturer-student ratio on programmes is around 1:25 compared to the 1:10 benchmark for excellence. Academics who teach on the programmes are clearly research active with some having published papers in leading international journals. There is, however, plenty of scope for improvement particularly at the highest international level. Out of more than 5000 papers published in six leading international peer-reviewed journals since each of them was established, only 23 of the papers have come from West Africa. The 23 papers are published by 28 academics based in 13 universities. Although some academics may publish their work in the plethora of journals that have proliferated in recent years, new generation researchers are encouraged to publish in more established journals. The analyses of 187 publications in the WABER conference proceedings revealed 18 research-active universities. Factors like quality of teaching, research and lecturer-student ratio, etc count in the ranking of universities. The findings lay bare some of the areas that should be addressed to improve the landscape of higher education in West Africa.

Energy at work: a measurement validation and linkage to unit effectiveness

We introduce the notion that the energy of individuals can manifest as a higher-level, collective construct. To this end, we conducted four independent studies to investigate the viability and importance of the collective energy construct as assessed by a new survey instrument—the productive energy measure (PEM). Study 1 (n = 2208) included exploratory and confirmatory factor analyses to explore the underlying factor structure of PEM. Study 2 (n = 660) cross-validated the same factor structure in an independent sample. In study 3, we administered the PEM to more than 5000 employees from 145 departments located in five countries. Results from measurement invariance, statistical aggregation, convergent, and discriminant-validity assessments offered additional support for the construct validity of PEM. In terms of predictive and incremental validity, the PEM was positively associated with three collective attitudes—units' commitment to goals, the organization, and overall satisfaction. In study 4, we explored the relationship between the productive energy of firms and their overall performance. Using data from 92 firms (n = 5939employees), we found a positive relationship between the PEM (aggregated to the firm level) and the performance of those firms. Copyright © 2011 John Wiley & Sons, Ltd.

Geoarchaeology and the value of multidisciplinary palaeoenvironmental approaches: a case study from the Tehran Plain, Iran

Tepe Pardis, a significant Neolithic–Chalcolithic site on the Tehran Plain in Iran, is, like many sites in the area, under threat from development. The site contains detailed evidence of (1) the Neolithic–Chalcolithic transition, (2) an Iron Age cemetery and (3) how the inhabitants adapted to an unstable fan environment through resource exploitation (of clay deposits for relatively large-scale ceramic production by c. 5000 BC, and importantly, possible cutting of artificial water channels). Given this significance, models have been produced to better understand settlement distribution and change in the region. However, these models must be tied into a greater understanding of the impact of the geosphere on human development over this period. Forming part of a larger project focusing on the transformation of simple, egalitarian Neolithic communities into more hierarchical Chalcolithic ones, the site has become the focus of a multidisciplinary project to address this issue. Through the combined use of sedimentary and limited pollen analysis, radiocarbon and optically stimulated luminescence dating (the application of the last still rare in Iran), a greater understanding of the impact of alluvial fan development on human settlement through alluviation and the development of river channel sequences is possible. Notably, the findings presented here suggest that artificial irrigation was occurring at the site as early as 6.7±0.4 ka (4300–5100 BC).

From wild horses to domestic horses: a European perspective

There is a period of some 5000 years or so in the prehistory of Europe when horse populations were greatly depleted and perhaps even disappeared in many places. Before this time, during the Upper Palaeolithic, wild horses were common; after, during the Bronze Age, domestic horses were being raised and used across Europe. What happened in between is uncertain, in part because of the sketchy archaeological record. Debates continue as to the origins (the when, where and how) of Europe's domestic horses, including whether horse husbandry dispersed only from habitats favourable to horses on the Eurasian steppes or whether there was local domestication in temperate Europe. This paper reviews the evidence for the transition from wild horses to domestic horses in Europe.

A comparison of the Thlaspi caerulescens and Thlaspi arvense shoot transcriptomes

Whole-genome transcriptome profiling is revealing how biological systems are regulated at the transcriptional level. This study reports the development of a robust method to profile and compare the transcriptomes of two nonmodel plant species, Thlaspi caerulescens, a zinc (Zn) hyperaccumulator, and Thlaspi arvense, a nonhyperaccumulator, using Affymetrix Arabidopsis thaliana ATH1-121501 GeneChip (R) arrays (Affymetrix, Santa Clara, CA, USA). Transcript abundance was quantified in the shoots of agar- and compost-grown plants of both species. Analyses were optimized using a genomic DNA (gDNA)-based probe-selection strategy based on the hybridization efficiency of Thlaspi gDNA with corresponding A. thaliana probes. In silico alignments of GeneChip (R) probes with Thlaspi gene sequences, and quantitative real-time PCR, confirmed the validity of this approach. Approximately 5000 genes were differentially expressed in the shoots of T. caerulescens compared with T. arvense, including genes involved in Zn transport and compartmentalization. Future functional analyses of genes identified as differentially expressed in the shoots of these closely related species will improve our understanding of the molecular mechanisms of Zn hyperaccumulation.

Holocene alluvial environments at Barking, Lower Thames Valley (London, UK)

Deposit modelling based on archived borehole logs supplemented by a small number of dedicated boreholes is used to reconstruct the main boundary surfaces and the thickness of the main sediment units within the succession of Holocene alluvial deposits underlying the floodplain in the Barking Reach of the Lower Thames Valley. The basis of the modelling exercise is discussed and the models are used to assess the significance of floodplain relief in determining patterns of sedimentation. This evidence is combined with the results of biostratigraphical and geochronological investigations to reconstruct the environmental conditions associated with each successive stage of floodplain aggradation. The two main factors affecting the history and spatial pattern of Holocene sedimentation are shown to be the regional behaviour of relative sea level and the pattern of relief on the surface of the sub-alluvial, Late Devensian Shepperton Gravel. As is generally the case in the Lower Thames Valley, three main stratigraphic units are recognised, the Lower Alluvium, a peat bed broadly equivalent to the Tilbury III peat of Devoy (1979) and an Upper Alluvium. There is no evidence to suggest that the floodplain was substantially re-shaped by erosion during the Holocene. Instead, the relief inherited from the Shepperton Gravel surface was gradually buried either by the accumulation of peat or by deposition of fine-grained sediment from suspension in standing or slow-moving water. The palaeoenvironmental record from Barking confirms important details of the Holocene record observed elsewhere in the Lower Thames Valley, including the presence of Taxus in the valley-floor fen carr woodland between about 5000 and 4000 cal BP, and the subsequent growth of Ulmus on the peat surface.

On the barrier properties of the cornea: a microscopy study of the penetration of fluorescently labeled nanoparticles, polymers, and sodium fluorescein

Overcoming the natural defensive barrier functions of the eye remains one of the greatest challenges of ocular drug delivery. Cornea is a chemical and mechanical barrier preventing the passage of any foreign bodies including drugs into the eye, but the factors limiting penetration of permeants and nanoparticulate drug delivery systems through the cornea are still not fully understood. In this study, we investigate these barrier properties of the cornea using thiolated and PEGylated (750 and 5000 Da) nanoparticles, sodium fluorescein, and two linear polymers (dextran and polyethylene glycol). Experiments used intact bovine cornea in addition to bovine cornea de-epithelialized or tissues pretreated with cyclodextrin. It was shown that corneal epithelium is the major barrier for permeation; pretreatment of the cornea with β-cyclodextrin provides higher permeation of low molecular weight compounds, such as sodium fluorescein, but does not enhance penetration of nanoparticles and larger molecules. Studying penetration of thiolated and PEGylated (750 and 5000 Da) nanoparticles into the de-epithelialized ocular tissue revealed that interactions between corneal surface and thiol groups of nanoparticles were more significant determinants of penetration than particle size (for the sizes used here). PEGylation with polyethylene glycol of a higher molecular weight (5000 Da) allows penetration of nanoparticles into the stroma, which proceeds gradually, after an initial 1 h lag phase.

Upwelling O+ ion source characteristics

Recent observations from the Dynamics Explorer 1 (DE-1) spacecraft have shown that the dayside auroral zone is an important source of very low-energy superthermal O^+ ions for the polar magnetosphere. When observed at 2000- to 5000-km altitude, the core of the O^+ distribution exhibits transverse heating to energies on the order of 10 eV, significant upward heat flux, and subsonic upward flow at significant flux levels exceeding 10^8 cm^{-2}s^{-1}. The term "upwelling ions" has been adopted to label these flows, which stand out in sharp contrast to the light ion polar wind flows observed in the same altitude range in the polar cap and subauroral magnetosphere. We have chosen a typical upwelling ion event for detailed study, correlating retarding ion mass spectrometer observations of the low-energy plasma with energetic ion observations and local electromagnetic field observations. The upwelling ion signature is colocated with the magnetospheric cleft as marked by precipitating energetic magnetosheath ions. The apparent ionospheric heating is clearly linked with the magnetic field signatures of strong field-aligned currents in the vicinity of the dayside polar cap boundary. Electric field and ion plasma measurements indicate that a very strong and localized convection channel or jet exists coincident with the other signatures of this event. These observations indicate that transverse ion heating to temperatures on the order of 10^5 K in the 2000- to 5000-km ionosphere is an important factor in producing heavy ion outflows into the polar magnetosphere. This result contrasts with recent suggestions that electron heating to temperatures of order 10^4 K is the most important parameter with regard to O^+ outflow.

Late Quaternary lake-level record from northern Eurasia

Lake records from northern Eurasia show regionally coherent patterns of changes during the late Quaternary. Lakes peripheral to the Scandinavian ice sheet were lower than those today but lakes in the Mediterranean zone were high at the glacial maximum, reflecting the dominance of glacial anticyclonic conditions in northern Europe and a southward shift of the Westerlies. The influence of the glacial anticyclonic circulation attenuated through the late glacial period, and the Westerlies gradually shifted northward, such that drier conditions south of the ice sheet were confined to a progressively narrower zone and the Mediterranean became drier. The early Holocene shows a gradual shift to conditions wetter than present in central Asia, associated with the expanded Asian monsoon, and in the Mediterranean, in response to local, monsoon-type circulation. There is no evidence of mid-continental aridity in northern Eurasia during the mid-Holocene. In contrast, the circum-Baltic region was drier, reflecting the increased incidence of blocking anticyclones centered on Scandinavia in summer. There is a gradual transition to modern conditions after ca. 5000 yr B.P. Although these broad-scale patterns are interrupted by shorter term fluctuations, the long-term trends in lake behavior show a clear response to changes in insolation and glaciation.