1,116 research outputs found
Kinetics and Mechanisms of the Chromium(III) Reactions with 2,4- and 2,5-Dihydroxybenzoic Acids in Weak Acidic Aqueous Solutions
The reactions of 2,4- and 2,5-dihydroxybenzoic acids (dihydroxybenzoic acid, DHBA) with chromium(III) in weak acidic aqueous solutions have been shown to take place in at least two stages. The first stage of the reactions has an observed rate constant k1(obs) = k1[DHBA] + C and the corresponding activation parameters are ΔH1(2,4)≠ = 49, 5 kJ/mol−1, ΔS1(2,4)≠ = −103, 7 J mol−1 K−1, ΔH1(2,5)≠ = 60, 3 kJ/mol−1, and ΔS1(2,5)≠ = −68, 0 J mol−1 K−1. These are composite activation parameters and the breaking of the strong intramolecular hydrogen bonding in the two ligands is suggested to be the first step of the (composite) first stage of the reactions. The second stage is ligand concentration independent and is thus attributed to a chelation process. The corresponding activation parameters are ΔH2(2,4)≠ = 45, 13 kJ/mol−1, ΔS2(2,4)≠ = −185, 9 J mol−1 K−1, ΔH2(2,5)≠ = 54, 55 kJ/mol−1, and ΔS2(2,5)≠ = −154, 8 J mol−1 K−1. The activation parameters support an associative mechanism for the second stage of the reactions. The various substitution processes are accompanied by proton release, resulting in pH decrease
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Improved 2-D vector field reconstruction using virtual sensors and the Radon transform
This paper describes a method that allows one to recover both components of a 2-D vector field based on boundary information only, by solving a system of linear equations. The analysis is carried out in the digital domain and takes advantage of the redundancy in the boundary data, since these may be viewed as weighted sums of the local vector field’s Cartesian components. Furthermore, a sampling of lines is used in order to combine the available measurements along continuous tracing lines with the digitised 2-D space where the solution is sought. A significant enhancement in the performance of the proposed algorithm is achieved by using, apart from real data, also boundary data obtained at virtual sensors. The potential of the proposed method is demonstrated by presenting an example of vector field reconstruction
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Virtual sensors for 2D vector field tomography
We consider the application of tomography to the reconstruction of 2-D vector fields. The most convenient sensor configuration in such problems is the regular positioning along the domain boundary. However, the most accurate reconstructions are obtained by sampling uniformly the Radon parameter domain rather than the border of the reconstruction domain. This dictates a prohibitively large number of sensors and impractical sensor positioning. In this paper, we propose uniform placement of the sensors along the boundary of the reconstruction domain and interpolation of the measurements for the positions that correspond to uniform sampling in the Radon domain. We demonstrate that when the cubic spline interpolation method is used, a 60 times reduction in the number of sensors may be achieved with only about 10% increase in the error with which the vector field is estimated. The reconstruction error by using the same sensors and ignoring the necessity of uniform sampling in the Radon domain is in fact higher by about 30%. The effects of noise are also examined
Health and nutrition claims for infant formula: international cross sectional survey
Objectives To review available health and nutrition claims for infant formula products in multiple countries and to evaluate the validity of the evidence used for substantiation of claims. Design International cross sectional survey. Setting Public facing and healthcare professional facing company owned or company managed formula industry websites providing information about products marketed for healthy infants delivered at full term in 15 countries: Australia, Canada, Germany, India, Italy, Japan, Nigeria, Norway, Pakistan, Russia, Saudi Arabia, South Africa, Spain, the United Kingdom, and the United States in 2020-22. Main outcome measures Number and type of claims made for each product and ingredient. References cited were reviewed and risk of bias was assessed for registered clinical trials using the Cochrane risk of bias tool, and for systematic reviews using the Risk Of Bias in Systematic reviews tool. Results 757 infant formula products were identified, each with a median of two claims (range from 1 (Australia) to 4 (US)), and 31 types of claims across all products. Of 608 products with ≥1 claims, the most common claim types were “helps/supports development of brain and/or eyes and/or nervous system” (323 (53%) products, 13 ingredients), “strengthens/supports a healthy immune system” (239 (39%) products, 12 ingredients), and “helps/supports growth and development” (224 (37%) products, 20 ingredients). 41 groups of ingredients were associated with ≥1claims, but many claims were made without reference to a specific ingredient (307 (50%) products). The most common groups of ingredients cited in claims were long chain polyunsaturated fatty acids (278 (46%) products, 9 different claims); prebiotics, probiotics, or synbiotics (225 (37%) products, 19 claims); and hydrolysed protein (120 (20%) products, 9 claims). 161/608 (26%) products with ≥1 claims provided a scientific reference to support the claim—266 unique references were cited for 24 different claim types for 161 products. The reference types most frequently cited were clinical trials (50%, 134/266) and reviews (20%, 52/266). 28% (38/134) of referenced clinical trials were registered, 14% (19/134) prospectively. 58 claims referred to 32 registered clinical trials, of which 51 claims (27 trials) related to a randomised comparison. 46 of 51 claims (90%) referenced registered clinical trial outcomes at high risk of bias, and all cited systematic reviews and pooled analyses, carried a high risk of bias. Conclusions Most infant formula products had at least one health and nutrition claim. Multiple ingredients were claimed to achieve similar health or nutrition effects, multiple claims were made for the same ingredient type, most products did not provide scientific references to support claims, and referenced claims were not supported by robust clinical trial evidence
A national register for surveillance of inherited disorders: beta thalassaemia in the United Kingdom
OBJECTIVE: To demonstrate the value of a national register for surveillance of services for an inherited disorder. METHODS: Data from the United Kingdom Thalassaemia Register and the United Kingdom Register of Prenatal Diagnosis for Haemoglobin Disorders were combined in a database; these registers include all fetuses known to have been diagnosed with beta thalassaemia major, beta thalassaemia intermedia, or haemoglobin E/beta thalassaemia in the United Kingdom. Data were extracted to show outcomes (selective abortion or live birth) of all fetuses and the status of those born with a disorder (alive, dead, successful bone marrow transplant, or lost to follow-up) by parents' region of residence and ethnicity. FINDINGS: At the end of 1999 the register included 1074 patients, 807 of whom were alive and residing in the United Kingdom. A successful bone marrow transplant has been performed for 117 out of 581 (20%) patients born since 1975. Residents of Pakistani origin are now the main group at risk in the United Kingdom, replacing residents of Cypriot origin. This has led to a marked shift in the need for services from the south-east of England to the Midlands and the north of England. Despite the acceptability of prenatal diagnosis, the proportion of affected births remains 50% higher than would be expected, reflecting a widespread failure to deliver timely screening and counselling to carriers. Even though effective treatment is available the annual number of deaths is rising, indicating that better tolerated treatments are needed. CONCLUSION: A national diagnosis register is a powerful instrument for monitoring the treatment and prevention of inherited disorders and for highlighting correctable shortcomings. In view of the increasing possibilities for genetic screening there is a strong case for central funding for such databases within modern health services
Kinetics and Mechanism of the Reaction between Chromium(III) and 2,3-Dihydroxybenzoic Acid in Weak Acidic Aqueous Solutions
The reaction between chromium(III) and 2,3-dihydroxybenzoic acid (2,3-DHBA) takes place in at least three stages, involving various intermediates. The ligand (2,3-DHBA)-to-chromium(III) ratio in the final product of the reaction is 1 : 1. The first stage is suggested to be the reaction of [Cr(H2O)5(OH)]2+ with the ligand in weak acidic aqueous solutions that follows an Id mechanism. The second and third stages do not depend on the concentrations of chromium(III), and their activation parameters are ΔH≠2(obs) = 61.2 ± 3.1 kJmol−1, ΔS≠2(obs) = −91.1 ± 11.0 JK−1mol−1, ΔH≠3(obs) = 124.5 ± 8.7 kJmol−1, and ΔS≠3(obs) = 95.1 ± 29.0 JK−1mol−1. These two stages are proposed to proceed via associative mechanisms. The positive value of ΔS≠3(obs) can be explained by the opening of a four-membered ring (positive entropy change) and the breaking of a hydrogen bond (positive entropy change) at the associative step of the replacement of the carboxyl group by the hydroxyl group at the chromium(III) center (negative entropy change in associative mechanisms). The reactions are accompanied by proton release, as shown by the pH decrease
Kinetics and Mechanism of the Reaction between Chromium(III) and 3,4-Dihydroxy-Phenyl-Propenoic Acid (Caffeic Acid) in Weak Acidic Aqueous Solutions
Our study of the complexation of 3,4-dihydroxy-phenyl-propenoic acid by chromium(III) could give information on the way that this metal ion is available to plants. The reaction between chromium(III) and 3,4-dihydroxy-phenyl-propenoic acid in weak acidic aqueous solutions has been shown to take place by at least three stages. The first stage corresponds to substitution (Id mechanism) of water molecule from the Cr(H2O)5OH2+ coordination sphere by a ligand molecule. A very rapid protonation equilibrium, which follows, favors the aqua species. The second and the third stages are chromium(III) and ligand concentration independent and are attributed to isomerisation and chelation processes. The corresponding activation parameters are ΔH2(obs)≠ = 28.6 ± 2.9 kJ mol−1, ΔS2(obs)≠ = −220 ± 10 J K−1mol−1, ΔH3(obs)≠ = 62.9 ± 6.7 kJ mol−1 and ΔS3(obs)≠ = −121 ± 22 J K−1mol−1. The kinetic results suggest associative mechanisms for the two steps. The associatively activated substitution processes are accompanied by proton release causing pH decrease
Reaction of Chromium(III) with 3,4-Dihydroxybenzoic Acid: Kinetics and Mechanism in Weak Acidic Aqueous Solutions
The interactions between chromium(III) and 3,4-dihydroxybenzoic acid (3,4-DHBA) were studied resulting in the formation of oxygen-bonded complexes upon substitution of water molecules in the chromium(III) coordination sphere. The experimental results show that the reaction takes place in at least three stages, involving various intermediates. The first stage was found to be linearly dependent on ligand concentration k1(obs)′ = k0 + k1(obs)[3, 4-DHBA], and the corresponding activation parameters were calculated as follows: ΔH1(obs)≠ = 51.2 ± 11.5 kJ mol−1, ΔS1(obs)≠ = −97.3 ± 28.9 J mol−1 K−1 (composite activation parameters) . The second and third stages, which are kinetically indistinguishable, do not depend on the concentrations of ligand and chromium(III), accounting for isomerization and chelation processes, respectively. The corresponding activation parameters are ΔH2(obs)≠ = 44.5 ± 5.0 kJ mol−1, ΔS2(obs)≠ = −175.8 ± 70.3 J mol−1 K−1. The observed stages are proposed to proceed via interchange dissociative (Id, first stage) and associative (second and third stages) mechanisms. The reactions are accompanied by proton release, as is shown by the pH decrease
The role of reproductive timing as a driver of genetic differentiation in populations of Pacific herring
There is growing recognition that maintaining diversity in life history traits contributes to the sustainable management of wild populations. One important life history characteristic is reproductive phenology, and it has been shown that differences in the timing of reproduction can act as a barrier to gene flow between populations. If the difference in reproductive timing determines the level of connectivity, one would expect that genetic differentiation between populations would increase as a function of difference in reproductive date. This pattern, known as “isolation by time” (IBT), has been observed in wild populations of salmonids containing early and late runs. Pacific herring in the Salish Sea also exhibit a wide diversity of spawn times; some populations start reproducing as early as January and reproductive activity in the region continues through May. Here, we test whether these temporal differences in reproduction influence the genetic population structure of herring. We collected adult herring from seven different locations in the Salish Sea during active spawning events (N = 48 per site). Samples were sequenced using a restriction site-associated (RAD) approach and approximately 3,000 polymorphic loci were genotyped in each sample. We found a positive correlation between genetic differentiation and difference in spawn date, with evidence of migration between populations with similar spawn timing. Several loci exhibited exceptionally steep gradients in allele frequencies, including one locus linked to the photoperiodic regulation of reproduction. Our discovery of IBT in Pacific herring support the adaptive significance of spawn timing and underscore the importance of conserving spawning time diversity in Puget Sound herring
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