Examination of the Silver Colloid Binding Behavior of Disulfide-Tethered Bipyridine Ligands and Their fac-Tricarbonylrhenium(I) Complexes

The syntheses of 2,2'-bipyridin-5-ylmethyl-5-(1,2-dithiolan-3-yl)pentanoate (L1) and N-(2,2'-bipyridin-5-ylmethyl)-5-(1,2-dithiolan-3-yl)pentanamide (L2) and their neutral fac carbonylrhenium(I) complexes [Re(L1)(CO)(3)Br] and [Re(L2)(CO)(3)Br] are reported. The. electronic absorption and emission spectra of the complexes are similar to the spectrum of the reference compound [Re(bipy)(CO)(3)Br] and correlate well with the density functional theory calculations undertaken. The surface-enhanced Raman spectroscopy (SERS) spectra (excited at both 532 and 785 nm) of the ligands and complexes were examined and compared to the spectrum of ethyl 5-(1,2-dithiolan-3-yl)pentanoate (L3), revealing that there is very little contribution to the spectra of these species from the dithiolated alkyl chains. The spectra are dominated by the characteristic peaks of a metalated 2,2'-bipyridyl group,arising from the silver colloid/ion complexation, and the rhenium center. The rhenium complexes show weak SERS bands related to the CO stretches and a broad band at 510 cm(-1) assigned to Re-CO stretching. Concentration dependent studies, measured by the relative intensity of several assigned peaks, indicate that, as the surface coverage increases, the bipyridine moiety lifts off the surface In the case of L1 and L2, this gives rise to complexes with silver at low concentration, enhancing the signals observed, while for the tricarbonylbromorhenium complexes of these ligands, the presence of the disulfide tether allows an enhancement in the limits of detection of these surface-borne species of 20 times in the case of [ReL2(CO)(3)Br] over [Re(bipy)(CO)(3)Br].

Forensic examination of multilayer white paint by lateral scanning Raman spectroscopy

Multilayer samples of white architectural paint potentially have very high evidential value in forensic casework, because the probability that two unrelated samples will have the same sequence of layers is extremely low. However, discrimination between the different layers using optical microscopy is often difficult or impossible. Here, lateral scanning Raman spectroscopy has been used to chemically map the cross-sections of multilayer white paint chips. It was found that the spectra did allow the different layers to be delineated on the basis of their spectral features. The boundaries between different layers were not as sharp as expected, with transitions occurring over length scales of > 20 µm, even with laser spot diameters <4 µm. However, the blurring of the boundaries was not so large as to prevent recording and identification of spectra from each of the layers in the samples. This method clearly provides excellent discrimination between different multilayer white paint samples and can readily be incorporated into existing procedures for examination of paint transfer evidence.

Examination of the physical state of chlorhexidine within viscoelastic, bioadhesive semisolids using Raman spectroscopy

This study examined the effects of polymeric components on the physical state of chlorhexidine within bioadhesive, semisolid formulations using Raman spectroscopy. Semisolid formulations were prepared in which chlorhexidine base (CHX, 5%w/w, particle size

Perceived relevance and foods with health-related claims

Although consumer perception of the health claims and nutrition information has been studied widely there is relatively little understanding about the motivational factors underpinning claim perception. The objective of this study is to investigate how levels of perceived relevance influence consumers’ responses to health claims that either promise to reduce a targeted disease risk or improve well-being in comparison to other types of health-related messages, and how attitudes towards nutritionally healthy eating, functional food and previous experience relating to products with health claims affect the consumers’ perceptions of nutrition and health claims. The data (N=2385) were collected by paper and pencil surveys in Finland, the UK, Germany and Italy on a target group of consumers over 35 year old, solely or jointly responsible for the family’s food shopping. The results showed that relevance has a strong influence on perceptions of personal benefit and willingness to buy products with health claims. However the impact of relevance is much stronger when the health risks are relevant to self than when it is relevant to those close to oneself, especially when the claim promises a targeted risk reduction with detailed information about function and health outcome. Previous experience with products with health claims and interest in nutritionally healthy eating promoted the utility of all claims, regardless of whether they were health or nutrition claims. However, to be influenced by health claims consumers also need to have a positive attitude towards functional food products.

Is dieting behaviour decreasing in young adolescents?

Abstract Objective: To report trends in underweight, overweight and obesity in 12–15-year-old adolescents and examine changes in dieting behaviour, which have been less well documented. Design: Comparison of two independent representative cross-sectional surveys. Setting: Northern Ireland. Subjects: Weight and height were objectively measured in 1324 boys and 1160 girls in 1996 and 1274 boys and 1374 girls in 2007. Participants reported whether they were following any particular diet including a self-proposed or prescribed weight-reduction diet. Results: Overweight and obesity increased in girls from 15% to 23% and 2% to 6%, respectively. Increases were more modest in boys with overweight increasing from 13% to 18% and obesity from 3% to 6%. The proportion of underweight adolescents decreased from 9% to 6% in girls and 8% to 5% in boys. Evidence of social disparity was observed in girls from a manual socio-economic background, with overweight/obesity prevalence rates increasing from 21% to 36% compared with 15% to 26% in girls from a non-manual background. Despite these trends fewer adolescents, in particular girls, reported following weight-reduction diets (14% of overweight/obese girls in 2007 v. 21% in 1996; 8% of boys in 2007 v. 13% in 1996). Of these girls, the proportion from a manual background following weight-reduction diets decreased from 25% to 11%. Conclusions: Overweight and obesity are continuing to increase in adolescents despite government and media awareness strategies. There also appears to be reduced dieting behaviour, despite increasing body weight, particularly in girls from manual socio-economic backgrounds.

A New Model for Automated Examination Timetabling

Automated examination timetabling has been addressed by a wide variety of methodologies and techniques over the last ten years or so. Many of the methods in this broad range of approaches have been evaluated on a collection of benchmark instances provided at the University of Toronto in 1996. Whilst the existence of these datasets has provided an invaluable resource for research into examination timetabling, the instances have significant limitations in terms of their relevance to real-world examination timetabling in modern universities. This paper presents a detailed model which draws upon experiences of implementing examination timetabling systems in universities in Europe, Australasia and America. This model represents the problem that was presented in the 2nd International Timetabling Competition (ITC2007). In presenting this detailed new model, this paper describes the examination timetabling track introduced as part of the competition. In addition to the model, the datasets used in the competition are also based on current real-world instances introduced by EventMAP Limited. It is hoped that the interest generated as part of the competition will lead to the development, investigation and application of a host of novel and exciting techniques to address this important real-world search domain. Moreover, the motivating goal of this paper is to close the currently existing gap between theory and practice in examination timetabling by presenting the research community with a rigorous model which represents the complexity of the real-world situation. In this paper we describe the model and its motivations, followed by a full formal definition.

An evaluation of the effect of altering nutrition and nutritional strategies in early lactation on reproductive performance and estrous behavior of high-yielding Holstein-Friesian dairy cows

Reproductive performance in the high-yielding dairy cow has severely decreased in the last 40 yr. The aim of this study was to compare the effectiveness of 4 nutritional strategies in improving the reproductive performance of high-yielding dairy cows. It was hypothesized that offering cows a high-starch ration in early lactation would enhance the onset of luteal activity, and that decreasing the severity of negative energy balance in the early postcalving period would improve reproductive parameters. Nutritional regimens aimed at improving fertility were applied to 96 Holstein-Friesian dairy animals. Upon calving, animals were allocated in a balanced manner to one of 4 dietary treatments. Primiparous animals were balanced according to live weight, body condition score and calving date. Multiparous animals were balanced according to parity, previous lactation milk yield, liveweight, body condition score and calving date. Treatment 1 was based on an industry best practice diet (control) to contain 170 g of crude protein/kg of dry matter. Treatment 2 was an individual cow feeding strategy, whereby the energy balance (EB) of individual animals was managed so as to achieve a predetermined target daily EB profile (+/- 10 MJ/d). Treatment 3 was a high-starch/high-fat combination treatment, whereby an insulinogenic (high-starch) diet was offered in early lactation to encourage cyclicity and followed by a lipogenic (low-starch, high-fat) diet to promote embryo development. Treatment 4 was a low-protein diet, containing 140 g of crude protein/kg of dry matter, supplemented with protected methionine at an inclusion level of 40 g per animal per day. The nutritional strategies implemented in this study had no statistically significant effects on cow fertility measures, which included the onset of luteal activity, conception rate, in-calf rate, and the incidence of atypical cycles. The individual cow feeding strategy improved EB in early lactation but had no benefit on conception rate to first insemination. However, conception rate to second insemination, 100-d pregnancy rate (from the commencement of breeding), and overall pregnancy rate tended to be higher in this group. The high-starch/high-fat treatment tended to decrease the proportion of delayed ovulations and increase the proportion of animals cycling by d 50 postcalving. Animals that failed to conceive to first insemination had a significantly longer luteal phase in the first cycle postpartum and a longer inter-ovulatory interval in the second cycle postpartum. With regards to estrous behavior, results indicate that as the size of the sexually active group increased, the intensity of estrus and the expression of mounting or attempting to mount another cow also increased. Furthermore, cows that became pregnant displayed more intense estrous behavior than cows that failed to become pregnant.