A rheological and SAXS study of the lamellar order in a side-on liquid crystalline block copolymer

We study the structure and shear flow behavior of a side-on liquid crystalline triblock copolymer, named PBA-b-PA444-b-PBA (PBA is poly(butyl acrylate) and PA444 is a poly(acrylate) with a nematic liquid crystal side-on mesogen), in the self-assembled lamellar phase and in the disordered phase. Simultaneous oscillatory shear and small-angle X-ray scattering experiments show that shearing PBA-b-PA444-b-PBA at high frequency and strain amplitudes leads to the alignment of the lamellae with normals perpendicular to the shear direction and to the velocity gradient direction, i.e., in the perpendicular orientation. The order-to-disorder transition temperature (T-ODT) is independent of the applied strain, in contrast to results reported in the literature for coil-coil diblock copolymers, which show an increase in T-ODT with shear rate. It is possible that in our system, T-ODT does not depend on the applied strain because the fluctuations are weaker than those present in coil-coil diblock copolymer systems.

A reaction surface Hamiltonian study of malonaldehyde

We report calculations using a reaction surface Hamiltonian for which the vibrations of a molecule are represented by 3N-8 normal coordinates, Q, and two large amplitude motions, s(1) and s(2). The exact form of the kinetic energy operator is derived in these coordinates. The potential surface is first represented as a quadratic in Q, the coefficients of which depend upon the values of s(1),s(2) and then extended to include up to Q(6) diagonal anharmonic terms. The vibrational energy levels are evaluated by solving the variational secular equations, using a basis of products of Hermite polynomials and appropriate functions of s(1),s(2). Our selected example is malonaldehyde (N=9) and we choose as surface parameters two OH distances of the migrating H in the internal hydrogen transfer. The reaction surface Hamiltonian is ideally suited to the study of the kind of tunneling dynamics present in malonaldehyde. Our results are in good agreement with previous calculations of the zero point tunneling splitting and in general agreement with observed data. Interpretation of our two-dimensional reaction surface states suggests that the OH stretching fundamental is incorrectly assigned in the infrared spectrum. This mode appears at a much lower frequency in our calculations due to substantial transition state character. (c) 2006 American Institute of Physics.

Spectral invariant behavior of zenith radiance around cloud edges observed by ARM SWS

The ARM Shortwave Spectrometer (SWS) measures zenith radiance at 418 wavelengths between 350 and 2170 nm. Because of its 1-sec sampling resolution, the SWS provides a unique capability to study the transition zone between cloudy and clear sky areas. A spectral invariant behavior is found between ratios of zenith radiance spectra during the transition from cloudy to cloud-free. This behavior suggests that the spectral signature of the transition zone is a linear mixture between the two extremes (definitely cloudy and definitely clear). The weighting function of the linear mixture is a wavelength-independent characteristic of the transition zone. It is shown that the transition zone spectrum is fully determined by this function and zenith radiance spectra of clear and cloudy regions. An important result of these discoveries is that high temporal resolution radiance measurements in the clear-to-cloud transition zone can be well approximated by lower temporal resolution measurements plus linear interpolation.

Effect of abomasal glucose infusion on plasma concentrations of gut peptides in periparturient dairy cows

Six Holstein cows fitted with ruminal cannulas and permanent indwelling catheters in the portal vein, hepatic vein, mesenteric vein, and an artery were used to study the effects of abomasal glucose infusion on splanchnic plasma concentrations of gut peptides. The experimental design was a randomized block design with repeated measurements. Cows were assigned to one of 2 treatments: control or infusion of 1,500 g of glucose/d into the abomasum from the day of parturition to 29 d in milk. Cows were sampled 12 ± 6 d prepartum and at 4, 15, and 29 d in milk. Concentrations of glucose-dependent insulinotropic polypeptide, glucagon-like peptide 1(7–36) amide, and oxyntomodulin were measured in pooled samples within cow and sampling day, whereas active ghrelin was measured in samples obtained 30 min before and after feeding at 0800 h. Postpartum, dry matter intake increased at a lower rate with infusion compared with the control. Arterial, portal venous, and hepatic venous plasma concentrations of the measured gut peptides were unaffected by abomasal glucose infusion. The arterial, portal venous, and hepatic venous plasma concentrations of glucose-dependent insulinotropic polypeptide and glucagon-like peptide 1(7–36) amide increased linearly from 12 d prepartum to 29 d postpartum. Plasma concentrations of oxyntomodulin were unaffected by day relative to parturition. Arterial and portal venous plasma concentrations of ghrelin were lower postfeeding compared with prefeeding concentrations. Arterial plasma concentrations of ghrelin were greatest prepartum and lowest at 4 d postpartum, giving a quadratic pattern of change over the transition period. Positive portal venous-arterial and hepatic venous–arterial concentration differences were observed for glucagon-like peptide 1(7–36) amide. A negative portal venous–arterial concentration difference was observed for ghrelin pre-feeding. The remaining portal venous–arterial and hepatic venous–arterial concentration differences of gut peptides did not differ from zero. In conclusion, increased postruminal glucose supply to postpartum transition dairy cows reduced feed intake relative to control cows, but did not affect arterial, portal venous, or hepatic venous plasma concentrations of gut peptide hormones. Instead, gut peptide plasma concentrations increased as lactation progressed. Thus, the lower feed intake of postpartum dairy cows receiving abomasal glucose infusion was not attributable to changes in gut peptide concentrations.

Modulating self-assembly of a nanotape-forming peptide amphiphile with an oppositely charged surfactant

A peptide amphiphile (PA) C16-KTTKS, containing a pentapeptide headgroup based on a sequence from procollagen I attached to a hexadecyl lipid chain, self-assembles into extended nanotapes in aqueous solution. The tapes are based on bilayer structures, with a 5.2 nm spacing. Here, we investigate the effect of addition of the oppositely charged anionic surfactant sodium dodecyl sulfate (SDS) via AFM, electron microscopic methods, small-angle X-ray scattering and X-ray diffraction among other methods. We show that addition of SDS leads to a transition from tapes to fibrils, via intermediate states that include twisted ribbons. Addition of SDS is also shown to enhance the development of remarkable lateral ‘‘stripes’’ on the nanostructures, which have a 4 nm periodicity. This is ascribed to counterion condensation. The transition in the nanostructure leads to changes in macroscopic properties, in particular a transition from sol to gel is noted on increasing SDS (with a further reentrant transition to sol on further increase of SDS concentration). Formation of a gel may be useful in applications of this PA in skincare applications and we show that this can be controlled via development of a network of fine stranded fibrils.

Cnoc Coig: a Mesolithic shell midden assemblage

Recent work on a sample of the chipped stone from one of the late Mesolithic shell midden sites on the Inner Hebrides island of Oronsay has shown that the assemblage was created using bipolar and platform technologies, with an unexpected element of narrow blade technology shown in cores and core trimming elements, suggesting that there may have been links between this classic ‘Obanian’ assemblage and the more typical Mesolithic narrow blade technology. Findings raise questions about the relationship of settlement on the island to Mesolithic settlement rounds and to the transition to the Neolithic.

Dietary, lifestyle and clinico-pathological factors associated with APC mutations and promoter methylation in colorectal cancers from the EPIC-Norfolk Study

The tumour suppressor APC is the most commonly altered gene in colorectal cancer (CRC). Genetic and epigenetic alterations of APC may therefore be associated with dietary and lifestyle risk factors for CRC. Analysis of APC mutations in the extended mutation cluster region (codons 1276-1556) and APC promoter 1A methylation was performed on 185 archival CRC samples collected from participants of the European Prospective Investigation into Cancer (EPIC)-Norfolk Study, with the aim of relating these to high quality seven-day dietary and lifestyle data collected prospectively. Truncating APC mutations (APC+) and promoter 1A methylation (PM+) were identified in 43% and 23% of CRCs analysed, respectively. Distal CRCs were more likely than proximal CRCs to be APC+ or PM+ (P = 0.04). APC+ CRCs were more likely to be moderately/well differentiated and microsatellite stable than APC- CRCs (P = 0.05 and 0.03). APC+ CRC cases consumed more alcohol than their counterparts (P = 0.01) and PM+ CRC cases consumed lower levels of folate and fibre (P = 0.01 and 0.004). APC+ or PM+ CRC cases consumedhigher levels of processed meat and iron from red meat and red meat products (P=0.007 and 0.006). Specifically, CRC cases harbouring GC to AT transition mutations consumed higher levels of processed meat (35 versus 24 g/day, P = 0.04) and iron from red meat and red meat products (0.8 versus 0.6 mg/day, P = 0.05). In a logistic regression model adjusted for age, sex and cigarette smoking status, each 19g/day (1SD) increment increase in processed meat consumption was associated with cases with GC to AT mutations (OR 1.68, 95% CI 1.03-2.75). In conclusion, APC+ and PM+ CRCs may be influenced by diet and GC to AT mutations in APC are associated with processed meat consumption, suggesting a mechanistic link with dietary alkylating agents, such as N-nitroso compounds.

Self-assembly of a peptide amphiphile containing l-carnosine and its mixtures with a multilamellar vesicle forming lipid

The self-assembly of the peptide amphiphile (PA) hexadecyl-(β-alaninehistidine) is examined in aqueous solution, along with its mixtures with multilamellar vesicles formed by DPPC (dipalmitoyl phosphatidylcholine). This PA, denoted C16-βAH, contains a dipeptide headgroup corresponding to the bioactive molecule L-carnosine. It is found to selfassemble into nanotapes based on stacked layers of molecules. Bilayers are found to coexist with monolayers in which the PA molecules pack with alternating up−down arrangement so that the headgroups decorate both surfaces. The bilayers become dehydrated as PA concentration increases and the number of layers in the stack decreases to produce ultrathin nanotapes comprised of 2−3 bilayers. Addition of the PA to DPPC multilamellar vesicles leads to a transition to well-defined unilamellar vesicles. The unique ability to modulate the stacking of this PA as a function of concentration, combined with its ability to induce a multilamellar to unilamellar thinning of DPPC vesicles, may be useful in biomaterials applications where the presentation of the peptide function at the surface of self-assembled nanostructures is crucial.

Thinking out of the box – skills for work

Since the Dearing Report .1 there has been an increased emphasis on the development of employability and transferable (‘soft’) skills in undergraduate programmes. Within STEM subject areas, recent reports concluded that universities should offer ‘greater and more sustainable variety in modes of study to meet the changing demands of industry and students’.2 At the same time, higher education (HE) institutions are increasingly conscious of the sensitivity of league table positions on employment statistics and graduate destinations. Modules that are either credit or non-credit bearing are finding their way into the core curriculum at HE. While the UK government and other educational bodies argue the way forward over A-level reform, universities must also meet the needs of their first year cohorts in terms of the secondary to tertiary transition and developing independence in learning.

A comparison between ion characteristics observed by the POLAR and DMSP spacecraft in the high-latitude magnetosphere

We study here the injection and transport of ions in the convection-dominated region of the Earth’s magnetosphere. The total ion counts from the CAMMICE MICS instrument aboard the POLAR spacecraft are used to generate occurrence probability distributions of magnetospheric ion populations. MICS ion spectra are characterised by both the peak in the differential energy flux, and the average energy of ions striking the detector. The former permits a comparison with the Stubbs et al. (2001) survey of He2+ ions of solar wind origin within the magnetosphere. The latter can address the occurrences of various classifications of precipitating particle fluxes observed in the topside ionosphere by DMSP satellites (Newell and Meng, 1992). The peak energy occurrences are consistent with our earlier work, including the dawn-dusk asymmetry with enhanced occurrences on the dawn flank at low energies, switching to the dusk flank at higher energies. The differences in the ion energies observed in these two studies can be explained by drift orbit effects and acceleration processes at the magnetopause, and in the tail current sheet. Near noon at average ion energies of _1 keV, the cusp and open LLBL occur further poleward here than in the Newell and Meng survey, probably due to convectionrelated time-of-flight effects. An important new result is that the pre-noon bias previously observed in the LLBL is most likely due to the component of this population on closed field lines, formed largely by low energy ions drifting earthward from the tail. There is no evidence here of mass and momentum transfer from the solar wind to the LLBL by nonreconnection coupling. At higher energies (_2–20 keV), we observe ions mapping to the auroral oval and can distinguish between the boundary and central plasma sheets. We show that ions at these energies relate to a transition from dawnward to duskward dominated flow, this is evidence of how ion drift orbits in the tail influence the location and behaviour of the plasma populations in the magnetosphere.

The interplay of metal-atom ordering, Fermi leveltuning and thermoelectric properties in cobalt shandites Co3M2S2 (M = Sn, In)

A combination of structural, physical and computational techniques including powder X-ray and neutron diffraction, SQUID magnetometry, electrical and thermal transport measurements, DFT calculations and 119Sn Mössbauer and X-ray photoelec-tron spectroscopies has been applied to Co3Sn2-xInxS2 (0 ≤ x ≤ 2) in an effort to understand the relationship between metal-atom ordering and physical properties as the Fermi level is systematically varied. Whilst solid solution behavior is found throughout the composition region, powder neutron diffraction reveals that indium preferentially occupies an inter-layer site over an alternative kagome-like intra-layer site. DFT calculations indicate that this ordering, which leads to a lowering of energy, is related to the dif-fering bonding properties of tin and indium. Spectroscopic data suggest that throughout the composition range 0 ≤ x ≤ 2, all ele-ments adopt oxidation states that are significantly reduced from expectations based on formal charges. Chemical substitution ena-bles the electrical transport properties to be controlled through tuning of the Fermi level within a region of the density of states, which comprises narrow bands of predominantly Co d-character. This leads to a compositionally-induced double metal-to-semiconductor-to-metal transition. The marked increase in the Seebeck coefficient as the semiconducting region is approached leads to a substantial improvement in the thermoelectric figure of merit, ZT, which exhibits a maximum of ZT = 0.32 at 673 K. At 425 K, the figure of merit for phases in the region 0.8 ≤ x ≤ 0.85 is amongst the highest reported for sulphide phases, suggesting these materials may have applications in low-grade waste heat recovery.

Two case studies of sulfate scavenging processes in the Amazon region (Rondonia)

The scavenging processes of chemical species have been previously studied with numerical modeling, in order to understand the gas and particulate matter intra-reservoir transferences. In this study, the atmospheric (RAMS) and scavenging (B.V.2) models were used, in order to simulate sulfate concentrations in rainwater using scavenging processes as well as the local atmospheric conditions obtained within the LBA Project in the State of Rondonia, during a dry-to-wet transition season. Two case studies were conducted. The RAMS atmospheric simulation of these events presented satisfactory results, showing the detailed microphysical processes of clouds in the Amazonian region. On the other hand, with cloud entrainments, observed values have been overestimated. Modeled sulfate rainwater concentration, using exponential decay and cloud heights of 16 km and no entrainments, presented the best results, reaching 97% of the observed value. The results, using shape parameter 5, are the best, improving the overall result. (C) 2008 Elsevier Ltd. All rights reserved.

Melanopsin and Clock Genes: Regulation by Light and Endothelin in the Zebrafish ZEM-2S Cell Line

It is well known that clocks are present in brain regions other than the suprachiasmatic nucleus and in many peripheral tissues. In the teleost, Danio rerio, peripheral oscillators can be directly synchronized by light. Danio rerio ZEM-2S embryonic cells respond to light with differential growth: cells kept in constant light exhibited a strong inhibition of proliferation, whereas in cells kept in light:dark (LD) cycles (14L:10D and 10L:14D) or in constant darkness (DD), the doubling times were not statistically different. We demonstrated by RT-PCR followed by PCR that ZEM-2S cells express two melanopsins, Opn4x and Opn4m, and the six Cry genes. The presence of the protein OPN4x was demonstrated by immunocytochemistry. The pattern of temporal expression of the genes Opn4x, Per1, Cry1b, and Clock was studied in ZEM-2S cells kept for five days in 12L:12D or DD. In 12L:12D, the clock genes Per 1 and Cry1b exhibited robust circadian expression, while Opn4x and Clock expression seemed to vary in an ultradian pattern. Both Per1 and Cry1b genes had higher expression during the L phase; Clock gene had an increase in expression coincident with the D phase, and during the subjective night. In DD, the temporal variation of Per1 and Cry1b genes was greatly attenuated but not extinguished, and the higher expressions were shifted to the transition times between subjective day and night, demonstrating that Per and Cry1b were synchronized by the LD cycle. Clock and Opn4x kept the ultradian oscillation, but the rhythm was not statistically significant. As endothelins (ET) have been reported to be a potent stimulator of Per genes in rodents, we investigated the effect of endothelin on ZEM-2S cells, which express ETA receptors. Cells were kept in 12D:12L for five days, and then treated with 10-11 to 10-8M ET-1 for 24h. ET-1 exhibited a biphasic effect on Opn4x expression. At 10-11M, the hormone exerted a highly significant stimulation of Opn4x expression during the L phase and introduced a circadian oscillatory pattern. At 10-10M, a significant increase was seen at ZT21 and ZT0 (i.e., at the end of the D phase and beginning of the L phase), whereas 10-9 and 10-8M ET-1 inhibited the expression of Opn4x at most ZTs. Clock expression was unaffected by 10-8M ET-1; however, in the presence of lower concentrations, the expression was enhanced at some ZTs, strengthening the ultradian oscillation. ET-1 at 10-11 and 10-10M had no effect on Per1 circadian expression; however, 10-9 and 10-8M ET-1 reduced the amplitude of Per1 expression in the beginning of the L phase. ET-1 effects were less evident on Cry 1b. For both genes, the reduction in expression was not sufficient to abolish the circadian oscillatory pattern. Based on these results and data in the literature, a link between ET-1 stimulation of ETA receptors may be established by E4BP4 binding to the promoters and consequent inhibition of gene expression.

Iodide Transport Defect: Functional Characterization of a Novel Mutation in the Na(+)/I(-) Symporter 5 `-Untranslated Region in a Patient with Congenital Hypothyroidism

Context: Iodide transport defect (ITD) is an autosomal recessive disorder caused by impaired Na(+)/I(-) symporter (NIS)-mediated active iodide accumulation into thyroid follicular cells. Clinical manifestations comprise a variable degree of congenital hypothyroidism and goiter, and low to absent radioiodide uptake, as determined by thyroid scintigraphy. Hereditary molecular defects in NIS have been shown to cause ITD. Objective: Our objective was to perform molecular studies on NIS in a patient with congenital hypothyroidism presenting a clinical ITD phenotype. Design: The genomic DNA encoding NIS was sequenced, and an in vitro functional study of a newly identified NIS mutation was performed. Results: The analysis revealed the presence of an undescribed homozygous C to T transition at nucleotide -54 (-54C>T) located in the 5`-untranslated region in the NIS sequence. Functional studies in vitro demonstrated that the mutation was associated with a substantial decrease in iodide uptake when transfected into Cos-7 cells. The mutation severely impaired NIS protein expression, although NIS mRNA levels remained similar to those in cells transfected with wild-type NIS, suggesting a translational deficiency elicited by the mutation. Polysome profile analysis demonstrated reduced levels of polyribosomes-associated mutant NIS mRNA, consistent with reduced translation efficiency. Conclusions: We described a novel mutation in the 5`-untranslated region of the NIS gene in a newborn with congenital hypothyroidism bearing a clinical ITD phenotype. Functional evaluation of the molecular mechanism responsible for impaired NIS-mediated iodide concentration in thyroid cells indicated that the identified mutation reduces NIS translation efficiency with a subsequent decrease in protein expression and function. (J Clin Endocrinol Metab 96: E1100-E1107, 2011)

Characterization of Paracoccidioides brasiliensis COX9, COX12, and COX16 respiratory genes

Paracoccidioides brasiliensis is a thermo-dimorphic fungus that is the causative agent of paracoccidioidomyicosis (PCM), a human systemic granulomatous mycosis found in Latin America. Dimorphic transition from mycelium to yeast is required for establishing pathogenicity. Dimorphism is marked by changes in mitochondrial physiology, including modulation of respiration rate. In this work, we present the identification of three P. brasiliensis nuclear genes PbCOX9, PbCOX12, and PbCOX16 that code for structural sub-units and a putative assembly facilitator (PbCOX16) of the mitochondrial cytochrome c oxidase (COX), the terminal enzyme complex of the respiratory chain. We measured their expression pattern during the dimorphic transition from mycelium to yeast and back by real-time reverse transcription quantitative polymerase chain reaction (real-time RT-qPCR). Our results show that messages from these genes increase during the mycelium to yeast transition and decrease during the opposite conversion. This result supports active mitochondrial participation in the transition. Heterologous complementation of the corresponding Saccharomyces cerevisiae null mutant with the PbCOX9 gene was successfully obtained. (C) 2008 The British Mycological Society. Published by Elsevier Ltd. All rights reserved.