Stabilization of multi-stranded nucleic acid structures using 3'-S-phosphorothiolate linkages

3 '-S-Phosphorothiolate linkages incorporated into an oligodeoxynucleotide have been shown to stabilise duplex formation with a complementary RNA strand, but destabilise a duplex formed with a complementary DNA strand. The four-stranded i-motif structure is also stabilised this modification.

In vitro fermentation of a red wine extract by human gut microbiota: changes in microbial groups and formation of phenolic metabolites

An in vitro batch culture fermentation experiment was conducted with fecal inocula from three healthy volunteers in the presence and absence of a red wine extract. Changes in main bacterial groups were determined by FISH during a 48 h fermentation period. The catabolism of main flavonoids (i.e., flavan-3-ols and anthocyanins) and the formation of a wide a range of phenolic microbial metabolites were determined by a targeted UPLC-PAD-ESI-TQ MS method. Statistical analysis revealed that catechol/pyrocatechol, as well as 4-hydroxy-5-(phenyl)-valeric, 3- and 4-hydroxyphenylacetic, phenylacetic, phenylpropionic, and benzoic acids, showed the greatest increases in concentration during fermentation, whereas 5-(3′-hydroxyphenyl)-γ-valerolactone, its open form 4-hydroxy-5-(3′-hydroxyphenyl)-valeric acid, and 3,4-dihydroxyphenylacetic acid represented the largest interindividual variations in the catabolism of red wine polyphenols. Despite these changes, microbial catabolism did not produce significant changes in the main bacterial groups detected, although a slight inhibition of the Clostridium histolyticum group was observed.

Very high resolution bioclimatic zoning of Portuguese wine regions: present and future scenarios

Wine production is strongly affected by weather and climate and thus highly vulnerable to climate change. In Portugal, viticulture and wine production are an important economic activity. In the present study, current bioclimatic zoning in Portugal (1950–2000) and its projected changes under future climate conditions (2041–2070) are assessed through the analysis of an aggregated, categorized bioclimatic index (CatI) at a very high spatial resolution (near 1 km). CatI incorporates the most relevant bioclimatic characteristics of a given region, thus allowing the direct comparison between different regions. Future viticultural zoning is achieved using data from 13 climate model transient experiments following the A1B emission scenario. These data are downscaled using a two-step method of spatial pattern downscaling. This downscaling approach allows characterizing mesoclimatic influences on viticulture throughout Portugal. Results for the recent past depict the current spatial variability of Portuguese viticultural regions. Under future climate conditions, the current viticultural zoning is projected to undergo significant changes, which may represent important challenges for the Portuguese winemaking sector. The changes are quite robust across the different climate models. A lower bioclimatic diversity is also projected, resulting from a more homogeneous warm and dry climate in most of the wine regions. This will lead to changes in varietal suitability and wine characteristics of each region.

Ensemble projections for wine production in the Douro Valley of Portugal

Wine production is largely governed by atmospheric conditions, such as air temperature and precipitation, together with soil management and viticultural/enological practices. Therefore, anthropogenic climate change is likely to have important impacts on the winemaking sector worldwide. An important winemaking region is the Portuguese Douro Valley, which is known by its world-famous Port Wine. The identification of robust relationships between atmospheric factors and wine parameters is of great relevance for the region. A multivariate linear regression analysis of a long wine production series (1932–2010) reveals that high rainfall and cool temperatures during budburst, shoot and inflorescence development (February-March) and warm temperatures during flowering and berry development (May) are generally favourable to high production. The probabilities of occurrence of three production categories (low, normal and high) are also modelled using multinomial logistic regression. Results show that both statistical models are valuable tools for predicting the production in a given year with a lead time of 3–4 months prior to harvest. These statistical models are applied to an ensemble of 16 regional climate model experiments following the SRES A1B scenario to estimate possible future changes. Wine production is projected to increase by about 10 % by the end of the 21st century, while the occurrence of high production years is expected to increase from 25 % to over 60 %. Nevertheless, further model development will be needed to include other aspects that may shape production in the future. In particular, the rising heat stress and/or changes in ripening conditions could limit the projected production increase in future decades.

Statistical modelling of grapevine yield in the Port Wine region under present and future climate conditions

The impact of projected climate change on wine production was analysed for the Demarcated Region of Douro, Portugal. A statistical grapevine yield model (GYM) was developed using climate parameters as predictors. Statistically significant correlations were identified between annual yield and monthly mean temperatures and monthly precipitation totals during the growing cycle. These atmospheric factors control grapevine yield in the region, with the GYM explaining 50.4% of the total variance in the yield time series in recent decades. Anomalously high March rainfall (during budburst, shoot and inflorescence development) favours yield, as well as anomalously high temperatures and low precipitation amounts in May and June (May: flowering and June: berry development). The GYM was applied to a regional climate model output, which was shown to realistically reproduce the GYM predictors. Finally, using ensemble simulations under the A1B emission scenario, projections for GYM-derived yield in the Douro Region, and for the whole of the twenty-first century, were analysed. A slight upward trend in yield is projected to occur until about 2050, followed by a steep and continuous increase until the end of the twenty-first century, when yield is projected to be about 800 kg/ha above current values. While this estimate is based on meteorological parameters alone, changes due to elevated CO2 may further enhance this effect. In spite of the associated uncertainties, it can be stated that projected climate change may significantly benefit wine yield in the Douro Valley.

New wine into old skins: the enactment of literacy policy in Singapore

To better comprehend how educational reforms and classroom practice interconnect, we need to understand the epistemic environments created for learning, as well as the pedagogical activities and the modes of classroom discourse related to these activities. This article examines how a particular innovation in English literacy, Strategies for English Language Learning and Reading (STELLAR), has been implemented in Singapore. Outlining the broader curriculum initiatives, current literacy policy landscape and pedagogical effect of classroom discourse, we look at how English language teachers in grades 1 and 2 interpret the STELLAR curriculum. Situated within the larger international zeal of educational reform, Singapore presents a rich case for the study of policy–pedagogy initiatives, literacy instruction and cultural values. Adding to the existing policy enactment research, this investigation provides an opportunity to probe both the prospects and limitations of policy implementation associated with centralised educational structures, examination-oriented systems and societal cultural frameworks.

Tactical ethics: how the discourses of fairtrade and black economic empowerment change and interact in wine networks from South Africa to the UK.

This paper explores the spaces and power relations of ethical foodscapes. Ethics can offer a commodity a valuable unique selling point in a competitive marketplace but managing the changeable and multiple motivations for stakeholder participation throughout the commodity chain in order to utilise this opportunity is a complex negotiation. Through exploring the spaces and relations within three South African– UK ethical wine networks, the discursive tactics used to sustain these are uncovered. The discourses of Fairtrade, Black Economic Empowerment and organics are highly adaptive, interacting with each other in such a way as to always be contextually appealing. This ‘tactical mutability’ is combined with ‘scales of knowing’, which, this paper argues, are essential for network durability. ‘Scales of knowing’ refers to the recognition by stakeholders of the potential for different articulations of a discourse within the network, which combines with ‘tactical mutability’ to allow for a scalar, contextual and ’knowing’ (im)mutability to ensure the discourse’s continued appeal. However, even when one discourse is the ‘lead’ it always folds within it linkages to other ethical discourses at work, suggesting that ethical practice is mutually supportive discursively. This means that at the producer end ethical interactions may offer more capacity to enact genuine transformation than the solo operations of a discourse.

Phenolic acid intake, delivered via moderate champagne wine consumption, improves spatial working memory via the modulation of hippocampal and cortical protein expression/activation.

Aims: While much data exist for the effects of flavonoid-rich foods on spatial memory in rodents, there are no such data for foods/beverages predominantly containing hydroxycinnamates and phenolic acids. To address this, we investigated the effects of moderate Champagne wine intake, which is rich in these components, on spatial memory and related mechanisms relative to the alcohol- and energy-matched controls. Results: In contrast to the isocaloric and alcohol-matched controls, supplementation with Champagne wine (1.78 ml/kg BW, alcohol 12.5% vol.) for 6 weeks led to an improvement in spatial working memory in aged rodents. Targeted protein arrays indicated that these behavioral effects were paralleled by the differential expression of a number of hippocampal and cortical proteins (relative to the isocaloric control group), including those involved in signal transduction, neuroplasticity, apoptosis, and cell cycle regulation. Western immunoblotting confirmed the differential modulation of brain-derived neurotrophic factor, cAMP response-element-binding protein (CREB), p38, dystrophin, 2',3'-cyclic-nucleotide 3'-phosphodiesterase, mammalian target of rapamycin (mTOR), and Bcl-xL in response to Champagne supplementation compared to the control drink, and the modulation of mTOR, Bcl-xL, and CREB in response to alcohol supplementation. Innovation: Our data suggest that smaller phenolics such as gallic acid, protocatechuic acid, tyrosol, caftaric acid, and caffeic acid, in addition to flavonoids, are capable of exerting improvements in spatial memory via the modulation in hippocampal signaling and protein expression. Conclusion: Changes in spatial working memory induced by the Champagne supplementation are linked to the effects of absorbed phenolics on cytoskeletal proteins, neurotrophin expression, and the effects of alcohol on the regulation of apoptotic events in the hippocampus and cortex. Antioxid. Redox Signal. 00, 000-000.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297

Are we there yet? Exploring empowerment at the microscale in the South African wine industry

Empowerment is a standard but ambiguous element of development rhetoric and so, through the socially complex and contested terrain of South Africa, this paper explores its potential to contribute to inclusive development. Investigating micro-level engagements with the national strategy of Broad-Based Black Economic Empowerment (B-BBEE) in the South African wine industry highlights the limitations, but also potential, of this single domain approach. However, latent paternalism, entrenched interests and a ‘dislocated blackness’ maintain a complex racial politics that shapes both power relations and the opportunities for transformation within the industry. Nonetheless, while B-BBEE may not, in reality, be broad-based its manifestations are contributing to challenging racist structures and normalising changing attitudes. This paper concludes that, to be transformative, empowerment needs to be re-embedded within South Africa as a multi-scalar, multi-dimensional dialogue and, despite the continuation of structural constraints, positions the local as a critical scale at which to initiate broader social change.

Stabilization of the i-motif structure by the intra-strand cross-link formation

The i-motif structures are formed by oligonucleotides containing cytosine tracts under acidic conditions. The folding of the i-motif under physiological conditions is of great interest because of its biological role. In this study, we investigated the effect of the intra-strand cross-link on the stability of the i-motif structure. The 4-vinyl-substituted analog of thymidine (T-vinyl) was incorporated into the 5′-end of the human telomere complementary strand, which formed the intra-strand cross-link with the internal adenine. The intra-strand cross-linked i-motif displayed CD spectra similar to that of the natural i-motif at acidic pH, which was transformed into a random coil with the increasing pH. The pH midpoint for the transition from the i-motif to random coil increased from pH 6.1 for the natural one to pH 6.8 for the cross-linked one. The thermodynamic parameters were obtained by measuring the thermal melting behaviors by CD and UV, and it was determined that the intra-strand cross-linked i-motif is stabilized due to a favorable entropy effect. Thus, this study has clearly indicated the validity of the intra-strand cross-linking for stabilization of the i-motif structure.

Stereochemistry and thermal stability of tartaric acid on the intrinsically chiral Cu{531} surface

Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of coadsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups,which are rotatedwith respect to each other by 90°±≈15°within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a O_C_C_O or HO–HC_CH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.

Astringency reduction in red wine by whey proteins

Whey is a by-product of cheese manufacturing and therefore investigating new applications of whey proteins will contribute towards the valorisation of whey and hence waste reduction. This study shows for the first time a detailed comparison of the effectiveness of gelatin and β-lactoglobulin (β-LG) as fining agents. Gelatin was more reactive than whey proteins to tannic acid as shown by both the astringency method (with ovalbumin as a precipitant) and the tannins determination method (with methylcellulose as a precipitant). The two proteins showed similar selectivity for polyphenols but β-LG did not remove as much catechin. The fining agent was removed completely or to a trace level after centrifugation followed by filtration which minimises its potential allergenicity. In addition, improved understanding of protein–tannin interactions was obtained by fluorescence, size measurement and isothermal titration calorimetry (ITC). Overall this study demonstrates that whey proteins have the potential of reducing astringency in red wine and can find a place in enology.

Gaze stabilization testing: The efficiency and test-retest reliability of user operated control versus the parameter estimation (PEST) algorithm

The primary objective of this research study is to determine which form of testing, the PEST algorithm or an operator-controlled condition is most accurate and time efficient for administration of the gaze stabilization test