Reactive state selectivity in photodimerization through micellar counter-ion effects: photodimerization of acenaphthylenes

Photodimerization of acenaphthylene and 5,6-dichloroacenaphthylene solubilized in sodium dodecylsulphate (SDS), cetyltrimethylammonium chloride (CTAC), dodecyltrimethylammonium chloride (DTAC), cetyltrimethylammonium bromide (CTAB) and Triton X-100 micelles gives a mixture of cis and trans dimers. The magnitude of the cis:trans ratio is sensitive to the type of micelle used. In CTAB micelles the heavy atom effect of the bromide counter-ions leads to an increased triplet-derived trans dimer yield, whereas in micelles with light atom counter-ions (CTAC, DTAC and SDS) the singlet-derived cis dimer predominates.

Strong gravity and the Yukawa field

A study of strong gravity field coupled to the Yukawa field is carried out for a conformally flat space-time. A quantitative relation between the strong interaction coupling constantg 2/hstrokc and the strong gravity constants (Lambda f~1028 cm–2,G f ~6.6×1030 C.G.S. units) is obtained givingg 2/hstroksim17, which is of the right order of magnitude. This justifies the contention that strong gravity is relevant for elementary particles (e.g., hadrons).

Molecular vibrations and conformation of primary dithiocarbamate ester. Infrared and NMR studies on S-methyl dithiocarbamate

The i.r. spectra of a primary dithiocarbamate ester namely, S-methyl dithiocarbamate (SMDTC) and its N-dideuterated compound have been measured between 4000 and 30 cm−1. Spectra in solution and at liquid nitrogen temperature have also been obtained. Assignment of all the fundamentals has been proposed and supported from a full normal coordinate analysis. The band assignments for SMDTC have been compared with those of related molecules and the characteristic bands of primary thioamides are derived. Conformational flexibility of SMDTC has been examined by i.r. and proton NMR spectroscopy. The hindered rotation around the C---N bond has been studied by a complete line shape analysis. The magnitude of ---NH2 and ---CH3 torsional barriers is also estimated from vibrational frequencies and force constants.

Charge transfer complexes of crown ethers with neutral organic gyama-acceptor, 2-dicyanoethylene 1,3-indane dione

The interaction of benzo-15-crown-5, dibenzo-18-crown-6 and dibenzo-24-crown-8 with 2-dicyanoethylene 1,3-indane dione in CH2Cl2 has been described in terms of the formation of 1 : 1 molecular complexes. The magnitude of association constants and thermodynamic parameters indicate cooperative interactions of oxygens with the acceptors. The 1H and 13C NMR spectra of the complexes show that gyama-gyama interactions are a major source of ground state stabilization in these complexes.

FreeS: A fast algorithm to discover frequent free subtrees using a novel canonical form

Web data can often be represented in free tree form; however, free tree mining methods seldom exist. In this paper, a computationally fast algorithm FreeS is presented to discover all frequently occurring free subtrees in a database of labelled free trees. FreeS is designed using an optimal canonical form, BOCF that can uniquely represent free trees even during the presence of isomorphism. To avoid enumeration of false positive candidates, it utilises the enumeration approach based on a tree-structure guided scheme. This paper presents lemmas that introduce conditions to conform the generation of free tree candidates during enumeration. Empirical study using both real and synthetic datasets shows that FreeS is scalable and significantly outperforms (i.e. few orders of magnitude faster than) the state-of-the-art frequent free tree mining algorithms, HybridTreeMiner and FreeTreeMiner.

Soil N availability, rather than N deposition, controls indirect N2O emissions

Ammonia volatilised and re-deposited to the landscape is an indirect N2O emission source. This study established a relationship between N2O emissions, low magnitude NH4 deposition (0–30  kg N ha − 1 ), and soil moisture content in two soils using in-vessel incubations. Emissions from the clay soil peaked ( < 0.002 g N [ g soil ] − 1 min − 1 ) from 85 to 93% WFPS (water filled pore space), increasing to a plateau as remaining mineral-N increased. Peak N2O emissions for the sandy soil were much lower ( < 5 × 10 − 5 μg N [ g soil ] − 1 min − 1 ) and occurred at about 60% WFPS, with an indistinct relationship with increasing resident mineral N due to the low rate of nitrification in that soil. Microbial community and respiration data indicated that the clay soil was dominated by denitrifiers and was more biologically active than the sandy soil. However, the clay soil also had substantial nitrifier communities even under peak emission conditions. A process-based mathematical denitrification model was well suited to the clay soil data where all mineral-N was assumed to be nitrified ( R 2 = 90 % ), providing a substrate for denitrification. This function was not well suited to the sandy soil where nitrification was much less complete. A prototype relationship representing mineral-N pool conversions (NO3− and NH4+) was proposed based on time, pool concentrations, moisture relationships, and soil rate constants (preliminary testing only). A threshold for mineral-N was observed: emission of N2O did not occur from the clay soil for mineral-N <70 mg ( kg of soil ) − 1 , suggesting that soil N availability controls indirect N2O emissions. This laboratory process investigation challenges the IPCC approach which predicts indirect emissions from atmospheric N deposition alone.

Queensland Spanner Crab Fishery : Commercial quota setting for June 2015 – May 2016

The Australian fishery for spanner crabs is the largest in the world, with the larger Queensland (QLD) sector’s landings primarily exported live overseas and GVP valued ~A$5 million per year. Spanner crabs are unique in that they may live up to 15 years, significantly more than blue swimmer crabs (Portunus armatus) and mud crabs (Scylla serrata), the two other important crab species caught in Queensland. Spanner crabs are caught using a flat net called a dilly, on which the crabs becoming entangled via the swimming legs. Quota setting rules are used to assess and adjust total allowable harvest (quota) around an agreed target harvest of 1631 t and capped at a maximum of 2000 t. The quota varies based on catch rate indicators from the commercial fishery and a fishery-independent survey from the previous two years, compared to target reference points. Quota management applies only to ‘Managed Area A’ which includes waters between Rockhampton and the New South Wales (NSW) border. This report has been prepared to inform Fisheries Queensland (Department of Agriculture and Fisheries) and stakeholders of catch trends and the estimated quota of spanner crabs in Managed Area A for the forthcoming quota period (1 June 2015–31 May 2016). The quota calculations followed the methodology developed by the crab fishery Scientific Advisory Group (SAG) between November 2007 and March 2008. The total reported spanner crab harvest was 917 t for the 2014 calendar year, almost all of which was taken from Managed Area A. In 2014, a total of 59 vessels were active in the QLD fishery, the lowest number since the peak in 1994 of 262 vessels. Recent spanner crab harvests from NSW waters have been about 125 t per year. The spanner crab Managed Area A commercial standardised catch rate averaged 0.739 kg per net-lift in 2014, 24% below the target level of 1.043. Mean catch rates declined in the commercial fishery in 2014, although the magnitude of the decreases was highest in the area north of Fraser Island. The NSW–QLD survey catch rate in 2014 was 16.849 crabs per ground-line, 22% above the target level of 13.972. This represented a decrease in survey catch rates of 0.366 crabs per ground-line, compared to the 2013 survey. The Queensland spanner crab total allowable harvest (quota) was set at 1923 t in 2012 and 2013. In 2014, the quota was calculated at the base level of 1631 t. However, given that the 2012 fisheryindependent survey was not undertaken for financial reasons, stakeholders proposed that the total allowable commercial catch (TACC) be decreased to 1777 t; a level that was halfway between the 2012/13 quota of 1923 t and the recommended base quota of 1631 t. The results from the current analysis indicate that the quota for the 2015-2016 financial year be decreased from 1777 t to the base quota of 1631 t.

Changes in atmospheric concentrations of polycyclic aromatic hydrocarbons and polychlorinated biphenyls between the 1990s and 2010s in an Australian city and the role of bushfires as a source

Over recent decades, efforts have been made to reduce human exposure to atmospheric pollutants including polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) through emission control and abatement. Along with the potential changes in their concentrations resulting from these efforts, profiles of emission sources may have also changed over such extended timeframes. However relevant data are quite limited in the Southern Hemisphere. We revisited two sampling sites in an Australian city, where the concentration data in 1994/5 for atmospheric PAHs and PCBs were available. Monthly air samples from July 2013 to June 2014 at the two sites were collected and analysed for these compounds, using similar protocols to the original study. A prominent seasonal pattern was observed for PAHs with elevated concentrations in cooler months whereas PCB levels showed little seasonal variation. Compared to two decades ago, atmospheric concentrations of ∑13 PAHs (gaseous + particle-associated) in this city have decreased by approximately one order of magnitude and the apparent halving time ( t 1 / 2 ) was estimated as 6.2 ± 0.56 years. ∑6 iPCBs concentrations (median value; gaseous + particle-associated) have decreased by 80% with an estimated t 1 / 2 of 11 ± 2.9 years. These trends and values are similar to those reported for comparable sites in the Northern Hemisphere. To characterise emission source profiles, samples were also collected from a bushfire event and within a vehicular tunnel. Emissions from bushfires are suggested to be an important contributor to the current atmospheric concentrations of PAHs in this city. This contribution is more important in cooler months, i.e. June, July and August, and its importance may have increased over the last two decades.

Can technology provide a glimmer of hope for economic growth in the midst of chaos? A case of Zimbabwe

In this paper we examine the effect of technology on economic growth in Zimbabwe over the period 1975–2014 whilst accounting for structural breaks. We use the extended Cobb–Douglas type Solow (Q J Econ 70(1):65–94, 1956) framework and the ARDL bounds procedure to examine cointegration and short run and long run effects. Using unit root tests, we note that structural changes in Zimbabwe are generally marked by the period 1982 onwards. We find that mobile technology has a positive short-run (0.09 %) and long-run (0.08 %) impact on the output per capita. The structural changes post-1982 periods show positive impact in the short-run (0.06) and the long-run (0.09), whereas the coefficient of trend in the short-run (−0.03) and the long-run (−0.04) is negative. The Granger non-causality test shows a unidirectional causality from capital stock (investment) per capita to output per capita and a bi-directional causality between mobile cellular technology and output per capita. The plausible reasons for estimated magnitude effects and the direction of causality are explained for policy deliberation.

Effect of carbon equivalent and inoculation on residual stresses in grey iron castings

It is virtually impossible to produce castings free from internal stresses using conventional methods of founding. Castings with appreciable stresses distort during storage, transportation, machining and service. Though composition and melt treatment are known to affect the magnitude of residual stress in castings, the data on the effect of carbon equivalent and inoculation on the magnitude of residual stress in castings are limited. In the present investigation, an attempt is made to study (i) the effect of carbon equivalent on residual stress in cast iron castings, and (ii) the effect of inoculants such as calcium silicide and ferrosilicon on residual stress in iron castings in the carbon equivalent range 3.0–4.0%. The results of the investigation indicate the following: (i) the residual strains decrease linearly with increase in carbon equivalent in the uninoculated and inoculated irons; (ii) the tensile residual stresses decrease linearly with increase in carbon equivalent value of the uninoculated, calcium silicide-inoculated and ferrosilicon-inoculated cast iron castings; (iii) the ratio of UTS to residual stress increased on inoculating the grid castings. This increase is higher for calcium silicide-inoculated grids than for ferrosilicon-inoculated grid castings. This implies that from the residual stress point of view, inoculation of the iron with calcium silicide is beneficial.

Diurnal variation of anterior scleral and conjunctival thickness

Purpose To examine whether anterior scleral and conjunctival thickness undergoes significant diurnal variation over a 24-hour period. Methods Nineteen healthy young adults (mean age 22 ± 2 years) with minimal refractive error (mean spherical equivalent refraction -0.08 ± 0.39 D), had measures of anterior scleral and conjunctival thickness collected using anterior segment optical coherence tomography (AS-OCT) at seven measurement sessions over a 24-hour period. The thickness of the temporal anterior sclera and conjunctiva were determined at 6 locations (each separated by 0.5 mm) at varying distances from the scleral spur for each subject at each measurement session. Results Both the anterior sclera and conjunctiva were found to undergo significant diurnal variations in thickness over a 24-hour period (both p <0.01). The sclera and conjunctiva exhibited a similar pattern of diurnal change, with a small magnitude thinning observed close to midday, and a larger magnitude thickening observed in the early morning immediately after waking. The amplitude of diurnal thickness change was larger in the conjunctiva (mean amplitude 69 ± 29 μm) compared to the sclera (21 ± 8 μm). The conjunctiva exhibited its smallest magnitude of change at the scleral spur location (mean amplitude 56 ± 17 μm) whereas the sclera exhibited its largest magnitude of change at this location (52 ± 21 μm). Conclusions This study provides the first evidence of diurnal variations occurring in the thickness of the anterior sclera and conjunctiva. Studies requiring precise measures of these anatomical layers should therefore take time of day into consideration. The majority of the observed changes occurred in the early morning immediately after waking and were of larger magnitude in the conjunctiva compared to the sclera. Thickness changes at other times of the day were of smaller magnitude and generally not statistically significant.

Intermolecular potentials in the dimer, the excimers, and the dimer ions of ethylene

Calculations are reported on the interaction energies in the dimer, the excimers, and the dimer ions of ethylene. The various a- and u-electron terms for different conformations of the dimeric species are determined by using the exchange perturbation method. The results predict that the singlet excimer and the dimer cation are stable primarily because of the large magnitude of the exciton-resonance and charge-resonance terms, respectively, while the neutral dimer, the triplet excimer, and the dimer anion are weakly stable. The variations of the various energy terms with conformations suggest that these dimeric species cannot have identifical structure.

Measurements of partial discharges-corrections to erroneous counts occurring in a cumulative pulse-counting system

The discharge pulse rates at different magnitude levels are often used as criteria for monitoring the partial-discharge aging of insulation systems. Use of suggested corrections for errors in cumulative probability counting leads to better use of available counters.

Estrogen-induced synthesis of riboflavin-binding protein in immature chicks kinetics and hormonal specificity

The kinetics of estrogen-induced elevation in the plasma concentration of riboflavin-binding protein, a minor yolk constituent, was investigated in immature male chicks, using a specific and sensitive radioimmunoassay proceudre. Following a single injection of the hormone, the plasma riboflavin-binding protein content was enhanced several-fold at 6 h. reaching peak levels around 48 h and declining thereafter. A two-fold amplication of the response was evident on secondary stimulation with the hormone. A 4-h lag phase prior to onset of induction was noticed during both primary and secondary stimulat ions with the steroid hormone. The magnitude of the response was dependent on the hormonal dose whereas the initial lag phase and the time of peak riboflavin-binding protein accumulation were unaltered within the range of hormonal doses tested. The half-life of riboflavin-binding protein in the circulation was 10 h, as calculated from measurement of the rate of disappearance of exogenously administered 125I-labelled protein. Simultaneous administration of progestrone did bot affect the kinetics of riboflavin-binding protein production. On the other hand, the antiestrogens, cis- and trans-clomiphene citrates, given 30 min prior to estrogen and cycloheximide, effectively countered the hormone-induced riboflavin-binding protein elaboration. Both progesterone and the anti-esterogens per se were completely ineffective in substituting for estrogen in the inductive ptrocess.

Sleep quantity and quality during heat-based training and the effects of cold-water immersion recovery

- Introduction Heat-based training (HT) is becoming increasingly popular as a means of inducing acclimation before athletic competition in hot conditions and/or to augment the training impulse beyond that achieved in thermo-neutral conditions. Importantly, current understanding of the effects of HT on regenerative processes such as sleep and the interactions with common recovery interventions remain unknown. This study aimed to examine sleep characteristics during five consecutive days of training in the heat with the inclusion of cold-water immersion (CWI) compared to baseline sleep patterns. - Methods Thirty recreationally-trained males completed HT in 32 ± 1 °C and 60% rh for five consecutive days. Conditions included: 1) 90 min cycling at 40 % power at VO2max (Pmax) (90CONT; n = 10); 90 min cycling at 40 % Pmax with a 20 min CWI (14 ± 1 °C; 90CWI; n = 10); and 30 min cycling alternating between 40 and 70 % Pmax every 3 min, with no recovery intervention (30HIT; n = 10). Sleep quality and quantity was assessed during HT and four nights of 'baseline' sleep (BASE). Actigraphy provided measures of time in and out of bed, sleep latency, efficiency, total time in bed and total time asleep, wake after sleep onset, number of awakenings, and wakening duration. Subjective ratings of sleep were also recorded using a 1-5 Likert scale. Repeated measures analysis of variance (ANOVA) was completed to determine effect of time and condition on sleep quality and quantity. Cohen's d effect sizes were also applied to determine magnitude and trends in the data. - Results Sleep latency, efficiency, total time in bed and number of awakenings were not significantly different between BASE and HT (P > 0.05). However, total time asleep was significantly reduced (P = 0.01; d = 1.46) and the duration periods of wakefulness after sleep onset was significantly greater during HT compared with BASE (P = 0.001; d = 1.14). Comparison between training groups showed latency was significantly higher for the 30HIT group compared to 90CONT (P = 0.02; d = 1.33). Nevertheless, there were no differences between training groups for sleep efficiency, total time in bed or asleep, wake after sleep onset, number of awakenings or awake duration (P > 0.05). Further, cold-water immersion recovery had no significant effect on sleep characteristics (P > 0.05). - Discussion Sleep plays an important role in athletic recovery and has previously been demonstrated to be influenced by both exercise training and thermal strain. Present data highlight the effect of HT on reduced sleep quality, specifically reducing total time asleep due to longer duration awake during awakenings after sleep onset. Importantly, although cold water recovery accelerates the removal of thermal load, this intervention did not blunt the negative effects of HT on sleep characteristics. - Conclusion Training in hot conditions may reduce both sleep quantity and quality and should be taken into consideration when administering this training intervention in the field.