Structure of 2-(2,6-dimethoxyphenyl)-2,5- dimethylbicyclo[3.2.1]octane-6,8-dione

C18H2204, orthorhombic, P212~21, a = 7.343 (4), b = 11.251 (4), c = 19.357 (4)A, Z = 4, Dr, ' = 1.20, D e = 1.254 g cm -3, F(000) = 648, p(MoKa) = 0.94 cm -~. X-ray intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.052 (R w = 0.045) for 1053 observed reflections. The stereochemical configuration at C(2) has been shown to be 2-exo-methyl-2-endo-(2,6-dimethoxyphenyl), i.e. (3) in contrast to the structure (2) assigned earlier based on its ~H NMR data.

3 - 5-vuotiaiden lukemaan oppiminen : montessorivälineet kielellisen tietoisuuden ja varhaisen lukitaidon edistäjinä

Aims. The beginning point of this research was confusion between studies claiming, that children mature Metalinguistic to read at 6-7 of age, and the fact, that in Montessori playschools children easily start writing and reading at age 3 to 5. Aim was also find out how conception of slow Metalinguistic development has started, and if there is some evidence of phoneme awareness of reading of young children in the field of research of reading. Aim was also seek evidence of the sensitive period of reading as Montessori described it. The research also wanted to turn up, if phoneme awareness only develops in children, who work with graphemes and with reading, or could it be found in children, who do not. The mean was to research how the Montessori reading material supports child’s Metalinguistic development, when child begins learning to read. The research plans to represent knowledge about how young children learn to write and read. Methods. Research performed in ordinary kindergarten and in Montessori playschool in Espoo. In kindergarten observed six children, age 3-4, at eight grapheme-rhyme sessions from January to April 2007, and conducting a test based on Chaney’s (1992) study of phoneme awareness of young children. In Montessori kindergarten were observed 17 children about their phoneme awareness and reading competition from January 2007 to March 2008. Their developments in reading were also measured three times from 1.9.07 to 20.3.08 with classification constructed for this study, loosely based on Chall’s (1983) reading stages. The Montessori reading material was analyzed about the influence they have to a child’s Metalinguistic development. This was done based to theory and its concepts from the field of research of reading; phoneme awareness, morphological, syntactical and semantic consciousness. Results and conclusions. Research proved that children 3-5 have naturally developed phoneme awareness. In kindergarten and in Montessori playschool children between 2 and 4 could do phoneme synthesis, and in the latter they also could do phoneme segmentation of words. Montessori reading material guided children gradually, except to read, also to observe and absorb Metalinguistic knowledge. Children learned to write and read. At the last evaluating day almost 50 % of children write and read clauses or stories, and 82 % could read at least words. Children can develop Metalinguistic awareness, while using the Montessori materials for learning to write and read. To reach literacy is easy for children because of their phoneme awareness.

Aritmetiikasta algebraan : Muutoksia osaamisessa peruskoulun päättöluokalla 20 vuoden aikana

From Arithmetic to Algebra. Changes in the skills in comprehensive school over 20 years. In recent decades we have emphasized the understanding of calculation in mathematics teaching. Many studies have found that better understanding helps to apply skills in new conditions and that the ability to think on an abstract level increases the transfer to new contexts. In my research I take into consideration competence as a matrix where content is in a horizontal line and levels of thinking are in a vertical line. The know-how is intellectual and strategic flexibility and understanding. The resources and limitations of memory have their effects on learning in different ways in different phases. Therefore both flexible conceptual thinking and automatization must be considered in learning. The research questions that I examine are what kind of changes have occurred in mathematical skills in comprehensive school over the last 20 years and what kind of conceptual thinking is demonstrated by students in this decade. The study consists of two parts. The first part is a statistical analysis of the mathematical skills and their changes over the last 20 years in comprehensive school. In the test the pupils did not use calculators. The second part is a qualitative analysis of the conceptual thinking of pupils in comprehensive school in this decade. The study shows significant differences in algebra and in some parts of arithmetic. The largest differences were detected in the calculation skills of fractions. In the 1980s two out of three pupils were able to complete tasks with fractions, but in the 2000s only one out of three pupils were able to do the same tasks. Also remarkable is that out of the students who could complete the tasks with fractions, only one out of three pupils was on the conceptual level in his/her thinking. This means that about 10% of pupils are able to understand the algebraic expression, which has the same isomorphic structure as the arithmetical expression. This finding is important because the ability to think innovatively is created when learning the basic concepts. Keywords: arithmetic, algebra, competence

The effect of foliar sprays of the synthetic auxin 3-5-6 TPA, on fruit drop, fruit size and seed development in three lychee (Litchi chinensis) cultivars: Tai So, Fay Zee Sui and Kwai Mai Pink.

Fruit drop in lychee can cause major yield losses in Australia, the severity varying with cultivar and season. Research in China, South Africa and Israel has demonstrated the potential for synthetic auxins used as foliar sprays to reduce fruit drop in lychee. Trials were initiated in Australia to test the efficacy of the synthetic auxin, 3-5-6 Trichloro-2-phridyl-oxyacetic acid (3-5-6 TPA) at 50 ppm on the cultivars Tai So, Fay Zee Sui and Kwai Mai Pink. Results indicate that in most cases the TPA reduced natural fruit drop however the size of the fruit at the time of application affects the response and the ideal application time varies with cultivar; approximately 13 mm fruit length in 'Kwai Mai Pink', 20 mm in 'Fay Zee Sui' and 27 mm in 'Tai So'. If applied too early in 'Tai So', it caused an increase in fruit drop. The TPA was most effective when natural fruit drop was high, reducing fruit drop from 74.7 to 34.9% in 'Kwai Mai Pink' and least effective when natural fruit drop was low. An increase in the percentage of fruit with poorly developed (chicken tongue) seed and slightly larger fruit size was also observed in treated trees.

Wood properties and processing outcomes for plantation grown African mahogany (Khaya senegalensis) trees from Clare, Queensland (18 and 20 year-old trees) and Katherine, Northern Territory (14 year-old trees).

Khaya senegalensis, African mahogany, a high-value hardwood, was introduced in the Northern Territory (NT) in the 1950s; included in various trials there and at Weipa, Q in the 1960s-1970s; planted on ex mine sites at Weipa (160 ha) until 1985; revived in farm plantings in Queensland and in trials in the NT in the 1990s; adopted for large-scale, annual planting in the Douglas-Daly region, NT from 2006 and is to have the planted area in the NT extended to at least 20,000 ha. The recent serious interest from plantation growers, including Forest Enterprises Australia Ltd (FEA), has seen the establishment of some large scale commercial plantations. FEA initiated the current study to process relatively young plantation stands from both Northern Territory and Queensland plantations to investigate the sawn wood and veneer recovery and quality from trees ranging from 14 years (NT – 36 trees) to 18-20 years (North Queensland – 31 trees). Field measures of tree size and straightness were complemented with log end splitting assessment and cross-sectional disc sample collection for laboratory wood properties measurements including colour and shrinkage. End-splitting scores assessed on sawn logs were relatively low compared to fast grown plantation eucalypts and did not impact processing negatively. Heartwood proportion in individual trees ranged from 50% up to 92 % of butt cross-sectional disc area for the visually-assessed dark coloured central heartwood and lighter coloured transition wood combined. Dark central heartwood proportion was positively related to tree size (R2 = 0.57). Chemical tests failed to assist in determining heartwood – sapwood boundary. Mean basic density of whole disc samples was 658 kg/m3 and ranged among trees from 603 to 712 kg/m3. When freshly sawn, the heartwood of African mahogany was orange-red to red. Transition wood appeared to be pinkish and the sapwood was a pale yellow colour. Once air dried the heartwood colour generally darkens to pinkish-brown or orange-brown and the effect of prolonged time and sun exposure is to darken and change the heartwood to a red-brown colour. A portable colour measurement spectrophotometer was used to objectively assess colour variation in CIE L*, a* and b* values over time with drying and exposure to sunlight. Capacity to predict standard colour values accurately after varying periods of direct sunlight exposure using results obtained on initial air-dried surfaces decreased with increasing time to sun exposure. The predictions are more accurate for L* values which represent brightness than for variation in the a* values (red spectrum). Selection of superior breeding trees for colour is likely to be based on dried samples exposed to sunlight to reliably highlight wood colour differences. A generally low ratio between tangential and radial shrinkages was found, which was reflected in a low incidence of board distortion (particularly cupping) during drying. A preliminary experiment was carried out to investigate the quality of NIR models to predict shrinkage and density. NIR spectra correlated reasonably well with radial shrinkage and air dried density. When calibration models were applied to their validation sets, radial shrinkage was predicted to an accuracy of 76% with Standard Error of Prediction of 0.21%. There was also a strong predictive power for wood density. These are encouraging results suggesting that NIR spectroscopy has good potential to be used as a non-destructive method to predict shrinkage and wood density using 12mm diameter increment core samples. Average green off saw recovery was 49.5% (range 40 to 69%) for Burdekin Agricultural College (BAC) logs and 41.9% (range 20 to 61%) for Katherine (NT) logs. These figures are about 10% higher than compared to 30-year-old Khaya study by Armstrong et al. (2007) however they are inflated as the green boards were not docked to remove wane prior to being tallied. Of the recovered sawn, dried and dressed volume from the BAC logs, based on the cambial face of boards, 27% could potentially be used for select grade, 40% for medium feature grade and 26% for high feature grades. The heart faces had a slightly higher recovery of select (30%) and medium feature (43%) grade boards with a reduction in the volume of high feature (22%) and reject (6%) grade boards. Distribution of board grades for the NT site aged 14 years followed very similar trends to those of the BAC site boards with an average (between facial and cambial face) 27% could potentially be used for select grade, 42% for medium feature grade, 26% for high feature grade and 5% reject. Relatively to some other subtropical eucalypts, there was a low incidence of borer attack. The major grade limiting defects for both medium and high feature grade boards recovered from the BAC site were knots and wane. The presence of large knots may reflect both management practices and the nature of the genetic material at the site. This stand was not managed for timber production with a very late pruning implemented at about age 12 years. The large amount of wane affected boards is indicative of logs with a large taper and the presence of significant sweep. Wane, knots and skip were the major grade limiting defects for the NT site reflecting considerable amounts of sweep with large taper as might be expected in younger trees. The green veneer recovered from billets of seven Khaya trees rotary peeled on a spindleless lathe produced a recovery of 83% of green billet volume. Dried veneer recovery ranged from 40 to 74 % per billet with an average of 64%. All of the recovered grades were suitable for use in structural ply in accordance to AS/NZ 2269: 2008. The majority of veneer sheets recovered from all billets was C grade (27%) with 20% making D grade and 13% B grade. Total dry sliced veneer recovery from the logs of the two largest logs from each location was estimated to be 41.1%. Very positive results have been recorded in this small scale study. The amount of colour development observed and the very reasonable recoveries of both sawn and veneer products, with a good representation of higher grades in the product distribution, is encouraging. The prospects for significant improvement in these results from well managed and productive stands grown for high quality timber should be high. Additionally, the study has shown the utility of non-destructive evaluation techniques for use in tree improvement programs to improve the quality of future plantations. A few trees combined several of the traits desired of individuals for a first breeding population. Fortunately, the two most promising trees (32, 19) had already been selected for breeding on external traits, and grafts of them are established in the seed orchard.

Inference of the genetic architecture underlying BMI and height with the use of 20,240 sibling pairs

Evidence that complex traits are highly polygenic has been presented by population-based genome-wide association studies (GWASs) through the identification of many significant variants, as well as by family-based de novo sequencing studies indicating that several traits have a large mutational target size. Here, using a third study design, we show results consistent with extreme polygenicity for body mass index (BMI) and height. On a sample of 20,240 siblings (from 9,570 nuclear families), we used a within-family method to obtain narrow-sense heritability estimates of 0.42 (SE = 0.17, p = 0.01) and 0.69 (SE = 0.14, p = 6 x 10(-)(7)) for BMI and height, respectively, after adjusting for covariates. The genomic inflation factors from locus-specific linkage analysis were 1.69 (SE = 0.21, p = 0.04) for BMI and 2.18 (SE = 0.21, p = 2 x 10(-10)) for height. This inflation is free of confounding and congruent with polygenicity, consistent with observations of ever-increasing genomic-inflation factors from GWASs with large sample sizes, implying that those signals are due to true genetic signals across the genome rather than population stratification. We also demonstrate that the distribution of the observed test statistics is consistent with both rare and common variants underlying a polygenic architecture and that previous reports of linkage signals in complex traits are probably a consequence of polygenic architecture rather than the segregation of variants with large effects. The convergent empirical evidence from GWASs, de novo studies, and within-family segregation implies that family-based sequencing studies for complex traits require very large sample sizes because the effects of causal variants are small on average.

1H and 13C NMR spectral studies of C-2 substituted isomeric exo- and endo-5-methyl-bicyclo[3.2.1]octane-6,8-diones

A detailed analysis of the 1H and 13C NMR spectra of C-2 aryl and alkyl/desalkyl substituted isomeric exo- and endo-5-methylbicyclo[3.2.1]octane-6,8-diones is presented. The chemical shift of the C-5 angular methyl, the C-2 alkyl/olefinic (C-10)/C-2 methine protons, the aromatic proton shieldings and the characteristic AMX and ABX spectral pattern of the ketomethylene and bridgehead protons were found to be sensitive to the phenyl ring orientation (anisotropy). These distinctive features could be used for configurational distinction for this class of compounds. With increasing ortho-methoxy substitution on the phenyl ring, considerable deshilelding of the bridgehead proton was observed (ca. 0.6 ppm). Absence of the C-2 alkyl group in the desalkyl isomers resulted in substantial changes in the chemical shifts of different protons. A study of the NMR spectra of the corresponding bicyclic compounds with C-2 methoxy/hydroxy substitution instead of the aryl group revealed that the anisotropy of the phenyl ring and the electronegative oxygen substituents have opposite effects. The 13C NMR spectral assignment of each carbon resonance of C-2 aryl and alkyl/desalkyl substituted isomeric exo- and endo-5-methylbicyclo[3.2.1]octane-6,8-diones and the corresponding C-2 methoxy/hydroxy/chloro and methyl bicyclic compounds are reported. Additional ortho-methoxy substitution on the phenyl ring was found to produce considerable high field shifts of the C-10 and C-1 carbon resonances. A high-field shift was observed for the C-6 and C-8 carbonyl carbons, presumably due to 1,3-dicarbonyl interactions. The chemical shifts of C-1 aromatic, C-10 alkyl and C-2 carbons, which are sensitive to exo/endo isomerism, could be utilized in differentiating a pair of isomers.

Structure of 2-(2,6-Dimethoxyphenyl)-2,5-dimethylbicyclo[3.2. l]octane-6,8-dione

C18H2204, orthorhombic, P212~21, a = 7.343 (4), b = 11.251 (4), c = 19.357 (4)A, Z = 4, Dr, ' = 1.20, D e = 1.254 g cm -3, F(000) = 648, p(Mo Ka) = 0.94 cm -~. X-ray intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.052 (R w = 0.045) for 1053 observed reflections. The stereochemical configuration at C(2) has been shown to be 2-exo-methyl-2-endo- (2,6-dimethoxyphenyl), i.e. (3) in contrast to the structure (2) assigned earlier based on its ~H NMR data.

Plan zemelʻnogo uchastka Nº 20

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Long-term use of custom-made orthopedic shoes: A 1.5-year follow-up study

This study investigated long-term use of custom-made orthopedic shoes (OS) at 1.5 years follow-up. In addition, the association between short-term outcomes and long-term use was studied. Patients from a previously published study who did use their first-ever pair of OS 3 months after delivery received another questionnaire after 1.5 years. Patients with different pathologies were included in the study (n = 269, response = 86%). Mean age was 63 ± 14 years, and 38% were male. After 1.5 years, 87% of the patients still used their OS (78% frequently [4-7 days/week] and 90% occasionally [1-3 days/week]) and 13% of the patients had ceased using their OS. Patients who were using their OS frequently after 1.5 years had significantly higher scores for 8 of 10 short-term usability outcomes (p-values ranged from <0.001 to 0.046). The largest differences between users and nonusers were found for scores on the short-term outcomes of OS fit and communication with the medical specialist and shoe technician (effect size range = 0.16 to 0.46). We conclude that patients with worse short-term usability outcomes for their OS are more likely to use their OS only occasionally or not at all at long-term follow-up.

The Crystal and Molecular Structure of 4-Aza-5-oxo-tricyclo[4.4.0.03,8]decane (Aza-twistanone)

Die kristalline Struktur von Aza-twistanon wurde durch eine Röntgenstruktur-analyse untersucht. Die Kristalle gehören zur monoklinen Raumgruppe P21/n mit den Zelldimensionen a = 6,662(6), b = 13,36(2), c = 8,606(9) Å, = 98,97(2)°, V = 757 Å3, Z = 4. Die Struktur wurde mit Direktmethoden gelöst und bis zu R = 0,035 verfeinert (mittlere (c) = 0,003 Å3).Die cis-Amidgruppe ist relativ stark deformiert und hat einen Torsionswinkel C -C -N-C von 14,5(4)° (Deformation aus der Ebene c = 5,0(5)° und N = 13,5(4,0)°). Die gegenüberliegende äthylenbrücke weist einen Torsionswinkel von 25,1(5)° auf. Die entsprechenden Winkel in Twistan betragen je 20°. Das tricyclische Gerüst von Aza-twistanon hat approximative.

A novel fully validated LC–MS/MS method for quantification of pyridoxal-5′-phosphate concentrations in samples of human whole blood

Quantification of pyridoxal-5´-phosphate (PLP) in biological samples is challenging due to the presence of endogenous PLP in matrices used for preparation of calibrators and quality control samples (QCs). Hence, we have developed an LC-MS/MS method for accurate and precise measurement of the concentrations of PLP in samples (20 µL) of human whole blood that addresses this issue by using a surrogate matrix and minimizing the matrix effect. We used a surrogate matrix comprising 2% bovine serum albumin (BSA) in phosphate buffer saline (PBS) for making calibrators, QCs and the concentrations were adjusted to include the endogenous PLP concentrations in the surrogate matrix according to the method of standard addition. PLP was separated from the other components of the sample matrix using protein precipitation with trichloroacetic acid 10% w/v. After centrifugation, supernatant were injected directly into the LC-MS/MS system. Calibration curves were linear and recovery was > 92%. QCs were accurate, precise, stable for four freeze-thaw cycles, and following storage at room temperature for 17h or at -80 °C for 3 months. There was no significant matrix effect using 9 different individual human blood samples. Our novel LC-MS/MS method has satisfied all of the criteria specified in the 2012 EMEA guideline on bioanalytical method validation.

Early life determinants of atopy : A 20-year prospective follow-up study on unselected, healthy newborns

Atopy-related allergic diseases, i.e. allergic rhinoconjunctivitis, atopic dermatitis and asthma, have increased in frequency in the industrialized countries. In order to reverse this trend, effective preventive strategies need to be developed. This requires a better understanding of the early-life events leading to the expression of the atopic phenotype. The present study has aimed at defining early-life factors and markers associated with the subsequent development of allergic diseases in a cohort of 200 healthy, unselected Finnish newborns prospectively followed up from birth to age 20 years. Their mothers were encouraged to start and maintain exclusive breastfeeding as long as it was nutritionally sufficient for the infant. Consequently, all the infants received some duration of exclusive breastfeeding, 58% of the infants were on exclusive breastfeeding for the first 6 months of life, and 18% received this feeding at least for the first 9 months. Of the infants, 42% had a family history of allergy. After the first year of follow-up, the children were re-assessed at ages 5, 11 and 20 years with clinical examination, skin prick testing, and parental and personal interviews. Exclusive breastfeeding for over 9 months was associated with atopic dermatitis and symptoms of food hypersensitivity at age 5 years, and with symptoms of food hypersensitivity at age 11 years in the children with a familial allergy. Subjects with allergic symptoms or a positive skin prick test in childhood or adolescence had lower retinol concentrations during their infancy and childhood than others. An elevated cord serum immunoglobulin E concentration predicted subsequent atopic manifestations though with modest sensitivity. Children and adolescents with allergic symptoms, skin prick test positivity and an elevated IgE had lower total cholesterol levels in infancy and childhood than the nonatopic subjects. In conclusion, prolonging strictly exclusive breastfeeding for over 9 months of age was not of help in prevention of allergic symptoms; instead, it was associated with increased atopic dermatitis and food hypersensitivity symptoms in childhood. Due to the modest sensitivity, cord serum IgE is not an effective screening method for atopic predisposition in the general population. Retinol and cholesterol concentrations in infancy were inversely associated with the subsequent development of allergic symptoms. Based on these findings, it is proposed that there may be differences in the inborn regulation of retinol and cholesterol levels in children with and without a genetic susceptibility to atopy, and these may play a role in the development of atopic sensitization and allergic diseases.

Mixed Azide and 5-(Pyrimidyl)tetrazole Bridged Co(II)/Mn(II) Polymers: Synthesis, Crystal Structures, Ferroelectric and Magnetic Behavior

The reaction of pyrimidine-2-carbonitrile, NaN3 in the presence of Co(NO3)(2)center dot 6H(2)O or MnCl2 center dot 4H(2)O leads to the formation of complexes Co(pmtz)(mu(1,3)-N-3)(H2O)](n) (1) and Mn(pmtz)(mu(1,3)-N-3)(H2O)](n) (2) respectively, under hydrothermal condition pmtz =5-(pyrimidyl)tetrazolate]. These two complexes have been fully characterized by single crystal X-ray diffraction. Complex 1 crystallizes in a non-centrosymmetric space group Aba2 in the orthorhombic system and is found to exhibit ferroelectric behavior, whereas complex 2 crystallizes in the P2(1)/c space group in the monoclinic system. Variable temperature magnetic characterizations in the temperature range of 2-300 K indicate that complex 1 is a canted antiferromagnet (weak ferromagnet) with T-c = 15.9 K. Complex 1 represents a unique example of a multiferroic coordination polymer containing tetrazole as a co-ligand. Complex 2 is a one-dimensional chain of Mn(II) bridged by a well-known antiferromagnetic coupler end-to-end azido ligand. In contrast to the role played by the end-to-end azido pathway in most of the transition metal complexes, complex 2 showed unusual ferromagnetic behavior below 40 K because of spin canting.