Impact of a new mandatory reporting law on reporting and identification of child sexual abuse: A seven year time trend analysis

Child sexual abuse is widespread and difficult to detect. To enhance case identification, many societies have enacted mandatory reporting laws requiring designated professionals, most often police, teachers, doctors and nurses, to report suspected cases to government child welfare agencies. Little research has explored the effects of introducing a reporting law on the number of reports made, and the outcomes of those reports. This study explored the impact of a new legislative mandatory reporting duty for child sexual abuse in the State of Western Australia over seven years. We analysed data about numbers and outcomes of reports by mandated reporters, for periods before the law (2006-08) and after the law (2009-12). Results indicate that the number of reports by mandated reporters of suspected child sexual abuse increased by a factor of 3.7, from an annual mean of 662 in the three year pre-law period to 2448 in the four year post-law period. The increase in the first two post-law years was contextually and statistically significant. Report numbers stabilised in 2010-12, at one report per 210 children. The number of investigated reports increased threefold, from an annual mean of 451 in the pre-law period to 1363 in the post-law period. Significant decline in the proportion of mandated reports that were investigated in the first two post-law years suggested the new level of reporting and investigative need exceeded what was anticipated. However, a subsequent significant increase restored the pre-law proportion, suggesting systemic adaptive capacity. The number of substantiated investigations doubled, from an annual mean of 160 in the pre-law period to 327 in the post-law period, indicating twice as many sexually abused children were being identified.

What does “futility” mean? An empirical study of doctors’ perceptions

Objective(s) To describe how doctors define and use the terms “futility” and “futile treatment” in end-of-life care. Design, Setting, Participants A qualitative study using semi-structured interviews with 96 doctors across a range of specialties who treat adults at the end of life. Doctors were recruited from three large Australian teaching hospitals and were interviewed from May to July 2013. Results Doctors’ conceptions of futility focused on the quality and chance of patient benefit. Aspects of benefit included physiological effect, weighing benefits and burdens, and quantity and quality of life. Quality and length of life were linked, but many doctors discussed instances when benefit was determined by quality of life alone. Most doctors described the assessment of chance of success in achieving patient benefit as a subjective exercise. Despite a broad conceptual consensus about what futility means, doctors noted variability in how the concept was applied in clinical decision-making. Over half the doctors also identified treatment that is futile but nevertheless justified, such as short-term treatment as part of supporting the family of a dying person. Conclusions There is an overwhelming preference for a qualitative approach to assessing futility, which brings with it variation in clinical decision-making. “Patient benefit” is at the heart of doctors’ definitions of futility. Determining patient benefit requires discussions with patients and families about their values and goals as well as the burdens and benefits of further treatment.

Stereochemical Analysis of Higher α,α-Dialkylglycine Containing Peptides. Characterization of Local Helical Conformations at Dipropylglycine Residues and Observation of a Novel Hydrated Multiple β-Turn Structure in Crystals of a Glycine Rich Peptide

The peptide Boc-Gly-Dpg-Gly-Gly-Dpg-Gly-NHMe (1) has been synthesized to examine the conformational preferences of Dpg residues in the context of a poor helix promoting sequence. Single crystals of 1 were obtained in the space group P21/c with a = 13.716(2) Å, b = 12.960(2) Å, c = 22.266(4) Å, and β = 98.05(1)°; R = 6.3% for 3660 data with |Fo| > 4σ. The molecular conformation in crystals revealed that the Gly(1)-Dpg(2) segment adopts φ, ψ values distorted from those expected for an ideal type II‘ β-turn (φGly(1) = +72.0°, ψGly(1) = −166.0°; φDpg(2) = −54.0°, ψDpg(2) = −46.0°) with an inserted water molecule between Boc-CO and Gly(3)NH. The Gly(3)-Gly(4) segment adopts φ, ψ values which lie broadly in the right handed helical region (φGly(3) = −78.0°, ψGly(3) = −9.0°; φGly(4) = −80.0°, ψGly(4) = −18.0°). There is a chiral reversal at Dpg(5) which takes up φ, ψ values in the left handed helical region. The Dpg(5)-Gly(6) segment closely resembles an ideal type I‘ β-turn (φDpg(5) = +56.0°, ψDpg(5) = +32.0°; φGly(6) = +85.0°, ψGly(6) = −3.0°). Molecules of both chiral senses are found in the centrosymmetric crystal. The C-terminus forms a hydrated Schellman motif, with water insertion into the potential 6 → 1 hydrogen bond between Gly(1)CO and Gly(6)NH. NMR studies in CDCl3 suggest substantial retention of the multiple turn conformation observed in crystals. In solution the observed NOEs support local helical conformation at the two Dpg residues.

Synthesis of neoglycopeptides and analyses of their biodistributionin vivo to identify tissue specific uptake and novel putative membrane lectins

Complex typeN-linked oligosaccharides derived from fetuin, fibrinogen and thyroglobulin were coupled to acetyltyrosine affording a series of neoglycopeptides with retention of terminal structures and the beta-anomeric configuration of their reducing endN-acetylglycosamine residue. The neoglycopeptides thus synthesized could be labelled to high specific activities with125I in the aromatic side chain of tyrosine. Analysis of the fate of these neoglycopeptides in conjunction with inhibition with asialofetuin and oligosaccharides of defined structure in micein vivo revealed the uptake of galactosylated biantennary compound by kidneys, in addition to the known itinerary of triantennary galactosylated complex oligosaccharide from fetuin to liver and the galactosylated biantennary chain with fucosylation in the core to bone marrows. On the other hand, the agalacto, aglucosamino biantennary chains with and without fucosylation in the core region are taken up by submaxillary glands while the conserved trimannosyl core with fucose is primarily concentrated in stomach tissue. These studies thus define new routes for the uptake of complexN-linked glycans and also subserve to identify lectins presumably involved in their recognition.

Selective Homonuclear Decoupling in H-1 NMR: Application to Visualization of Enantiomers in Chiral Aligning Medium and Simplified Analyses of Spectra in Isotropic Solutions

The proton NMR spectral complexity arising due to severe overlap of peaks hampers their analyses in diverse situations, even by the application of two-dimensional experiments. The selective or complete removal of the couplings and retention of only the chemical shift interactions in indirect dimension aids in the simplification of the spectrum to a large extent with little investment of the instrument time. The present study provides precise enantiodiscrimination employing more anisotropic NMR parameters in the chiral liquid crystalline medium and differentiates the overlapped peaks of many organic molecules and peptides dissolved in isotropic solvents.

Hormones and Cuscuta development: IAA uptake transport and metabolism in relation to growth in the absence and presence of applied cytokinin

Transport of 1-14C-IAA in successive stem segments of Cuscuta was strictly basipetal in growing and non growing regions of the vine with a flux velocity of 10-12 mm/h (intercept method). This transport showed a distinct peaked profile, increasing from a low value at 10 mm from the apex to a maximum between 50 and 90 mm before declining to a low value again around 160 mm at which elongation growth ceased. The IAA transport profile paralleled the in vivo growth rate profile, though the latter peaked ahead of transport. A better correlation was observed between the profile of growth responsiveness of the vine to exogenous IAA application and the profile of IAA transport. Growth responsiveness was determined as the differential in growth rate of stem segments in vitro in the absence and presence of growth optimal concentration of IAA (10 μm). Retention of exogenous IAA in the stem was maximal where transport decreased, and this coincided with the region of maximal conjugation of applied 1-14C-IAA to aspartic acid to form indoleacetylaspartate (IAAsp). In addition to aspartate, IAA was conjugated to a small extent to an unidentified compound. IAA destruction by decarboxylation was greatest where transport was low, particularly in the nongrowing region, where lignification occurred (i.e., beyond 180 mm). At concentrations up to 20 μM, a pulse of 1-14C-IAA chased by "cold" IAA moved as a peak (with a peak displacement velocity of 12-18 mm/h) in the "growth" region of the vine, but became diffusionlike where growth either fell off steeply or ceased. At a higher (50 μM) IAA concentration, though uptake was not saturated, transport in the growth region became diffusionlike, indicating saturation of the system. Reduced IAA flux in the region where growth responsiveness to IAA declined coincided with the region of increased IAA conjugation. However, it cannot be concluded whether increased IAA conjugation was the cause or effect of decreased IAA flux. Application of benzyladenine to the vines in vivo, a treatment that elicited haustoria formation by 72 h, resulted in the inhibition of both IAA transport and elongation growth rate in the subapical region. In vitro treatment of vine segments with BA similarly increased IAA retention and decreased IAA transport. IAA loss was suppressed, and conjugation to IAAsp was enhanced. © 1989 Springer-Verlag New York Inc.

Sedimentary zooplankton remains as indicators of lake ecological quality and trophic structure

To protect and restore lake ecosystems under threats posed by the increasing human population, information on their ecological quality is needed. Lake sediments provide a data rich archive that allows identification of various biological components present prior to anthropogenic alterations as well as a constant record of changes. By providing a longer dimension of time than any ongoing monitoring programme, palaeolimnological methods can help in understanding natural variability and long-term ecological changes in lakes. As zooplankton have a central role in the lake food web, their remains can potentially provide versatile information on past trophic structure. However, various taphonomic processes operating in the lakes still raise questions concerning how subfossil assemblages reflect living communities. This thesis work aimed at improving the use of sedimentary zooplankton remains in the reconstruction of past zooplankton communities and the trophic structure in lakes. To quantify interspecific differences in the accumulation of remains, the subfossils of nine pelagic zooplankton taxa in annually laminated sediments were compared with monitoring results for live zooplankton in Lake Vesijärvi. This lake has a known history of eutrophication and recovery, which resulted from reduced external loading and effective fishing of plankti-benthivorous fish. The response of zooplankton assemblages to these known changes was resolved using annually laminated sediments. The generality of the responses observed in Lake Vesijärvi were further tested with a set of 31 lakes in Southern Finland, relating subfossils in surface sediments to contemporary water quality and fish density, as well as to lake morphometry. The results demonstrated differential preservation and retention of cladoceran species in the sediment. Daphnia, Diaphanosoma and Ceriodaphnia were clearly underrepresented in the sediment samples in comparison to well-preserved Bosmina species, Chydorus, Limnosida and Leptodora. For well-preserved species, the annual net accumulation rate was similar to or above the expected values, reflecting effective sediment focusing and accumulation in the deepest part of the lake. The decreased fish density and improved water quality led to subtle changes in zooplankton community composition. The abundance of Diaphanosoma and Limnosida increased after the reduction in fish density, while Ceriodaphnia and rotifers decreased. The most sensitive indicator of fish density was the mean size of Daphnia ephippia and Bosmina (E.) crassicornis ephippia and carapaces. The concentration of plant-associated species increased, reflecting expanding littoral vegetation along with increasing transparency. Several of the patterns observed in Lake Vesijärvi could also be found within the set of 31 lakes. According to this thesis work, the most useful cladoceran-based indices for nutrient status and planktivorous fish density in Finnish lakes were the relative abundances of certain pelagic taxa, and the mean size of Bosmina spp. carapaces, especially those of Bosmina (E.) cf. coregoni. The abundance of plant-associated species reflected the potential area for aquatic plants. Lake morphometry and sediment organic content, however, explained a relatively high proportion of the variance in the species data, and more studies are needed to quantify lake-specific differences in the accumulation and preservation of remains. Commonly occurring multicollinearity between environmental variables obstructs the cladoceran-based reconstruction of single environmental variables. As taphonomic factors and several direct and indirect structuring forces in lake ecosystems simultaneously affect zooplankton, the subfossil assemblages should be studied in a holistic way before making final conclusions about the trophic structure and the change in lake ecological quality.

Fly ash as a pre-filter material for the retention of lead ions

Clay liners have been widely used to contain toxic and hazardous waste materials. Clays absorb contaminant cations due to their exchange capacity. To improve the performance of the clay liner, fly ash, a waste material arising from the combustion of coal has been studied as a pre-filter material. In particular, the retention of lead by two different fly ashes was studied. The influence of pH on retention as well as leaching characteristics are also examined. The results obtained from the retention experiments by the permeameter method indicate that fly ash retains the lead ions through precipitation in the pores as well as onto the surface when the ambient pH value is more than 5.5, and through adsorption when the pH value is less than 5.5. It has been observed that fly ash did not release the retained lead ions when the pH value is between 3.5 and 10.0. Hence, the retention of lead ions by fly ash is likely to be permanent since the pH of most of the municipal landfill leachates are within 3.7 to 8.8. However, for highly acidic or alkaline leachates, the retained ions can get released.

Influence of pH on the retention of heavy metal ions by fly ash

Clay liners have been widely used to contain toxic and hazardous wastes. Clays adsorb the contaminant cations due to their exchange capacity. To improve the performance of the clay liner, fly ash, a waste material arising out of combustion of coal has been studied as a pre-filter material. The results indicate that fly ash has the potential to retain heavy metal ions. This study concerns the retention of zinc by fly ash. The influence of pH on retention as well as leaching characteristics are examined. The results obtained from the retention experiments by permeameter method indicate that fly ash retains the zinc ions through precipitation in the pores as well as onto the surface when the ambient pH value is more than 6.9, and only through adsorption when the pH value is less than 6.9. It has been observed that fly ash did not release the retained zinc ions when the pH value is between 3.5 and 10.0. Hence, the retention of zinc ions by fly ash is likely to be permanent since the pH of most of the landfill leachates are between 3.7 to 8.8.

Synthesis and characterization of porous flowerlike alpha-Fe2O3 nanostructures for supercapacitor application

Porous flower-like alpha-Fe2O3 nanostructures synthesized by an ethylene glycol mediated self-assembly process are crystalline and porous with BET surface area of 64.6 m(2) g(-1). The discharge capacitance is 127 F g(-1) when the electrodes are cycled in 0.5 M Na2SO3 at a current density of 1 A g(-1). Capacitance retention after 1000 cycles is about 80% of the initial capacitance. The high discharge capacitance and its retention are attributed to high surface area and porosity of the iron oxide. As the iron oxides are inexpensive, the nano alpha-Fe2O3 is expected to be of potential use for supercapacitor application.

Improved capacity and stability of integrated Li and Mn rich layered-spinel Li1.17Ni0.25Mn1.08O3 cathodes for Li-ion batteries

A Li-rich layered-spinel material with a target composition Li1.17Ni0.25Mn1.08O3 (xLiLi1/3Mn2/3]O-2.(1 - x) LiNi0.5Mn1.5O4, (x = 0.5)) was synthesized by a self-combustion reaction (SCR), characterized by XRD, SEM, TEM, Raman spectroscopy and was studied as a cathode material for Li-ion batteries. The Rietveld refinement results indicated the presence of monoclinic (LiLi1/3Mn2/3]O-2) (52%), spinel (LiNi0.5Mn1.5O4) (39%) and rhombohedral LiNiO2 (9%). The electrochemical performance of this Li-rich integrated cathode material was tested at 30 degrees C and compared to that of high voltage LiNi0.5Mn1.5O4 spinel cathodes. Interestingly, the layered-spinel integrated cathode material exhibits a high specific capacity of about 200 mA h g(-1) at C/10 rate as compared to 180 mA h g(-1) for LiNi0.5Mn1.5O4 in the potential range of 2.4-4.9 V vs. Li anodes in half cells. The layered-spinel integrated cathodes exhibited 92% capacity retention as compared to 82% for LiNi0.5Mn1.5O4 spinel after 80 cycles at 30 degrees C. Also, the integrated cathode material can exhibit 105 mA h g(-1) at 2 C rate as compared to 78 mA h g(-1) for LiNi0.5Mn1.5O4. Thus, the presence of the monoclinic phase in the composite structure helps to stabilize the spinel structure when high specific capacity is required and the electrodes have to work within a wide potential window. Consequently, the Li1.17Ni0.25Mn1.08O3 composite material described herein can be considered as a promising cathode material for Li ion batteries.

Molecular Dynamics Study of the Structure, Flexibility, and Hydrophilicity of PETIM Dendrimers: A Comparison with PAMAM Dendrimers

A new class of dendrimers, the poly(propyl ether imine) (PETIM) dendrimer, has been shown to be a novel hyperbranched polymer having potential applications as a drug delivery vehicle. Structure and dynamics of the amine terminated PETIM dendrimer and their changes with respect to the dendrimer generation are poorly understood. Since most drugs are hydrophobic in nature, the extent of hydrophobicity of the dendrimer core is related to its drug encapsulation and retention efficacy. In this study, we carry out fully atomistic molecular dynamics (MD) simulations to characterize the structure of PETIM (G2-G6) dendrimers in salt solution as a function of dendrimer generation at different protonation levels. Structural properties such as radius of gyration (R-g), radial density distribution, aspect ratio, and asphericity are calculated. In order to assess the hydrophilicity of the dendrimer, we compute the number of bound water molecules in the interior of dendrirner as well as the number of dendrimer-water hydrogen bonds. We conclude that PETIM dendrimers have relatively greater hydrophobicity and flexibility when compared with their extensively investigated PAMAM counterparts. Hence PETIM dendrimers are expected to have stronger interactions with lipid membranes as well as improved drug encapsulation and retention properties when compared with PAMAM dendrimers. We compute the root-mean-square fluctuation of dendrimers as well as their entropy to quantify the flexibility of the dendrimer. Finally we note that structural and solvation properties computed using force field parameters derived based on the CHARMM general purpose force field were in good quantitative agreement with those obtained using the generalized Amber force field (GAFF).

Luffa acutangula agglutinin: Primary structure determination and identification of a tryptophan residue involved in its carbohydrate-binding activity using mass spectrometry

A lectin from phloem exudates of Luffa acutangula (ridge gourd) was purified on chitin affinity chromatography and characterized for its amino acid sequence and to study the role of tryptophan in its activity. The purified lectin was subjected to various proteolytic digestions, and the resulting peptides were analyzed by liquid chromatography coupled electrospray ionization ion trap mass spectrometer. The peptide precursor ions were fragmented by collision-induced dissociation or electron transfer dissociation experiments, and a manual interpretation of MS/MS was performed to deduce amino acid sequence. This gave rise to almost complete sequence coverage of the lectin which showed high-sequence similarity with deduced sequences of phloem lectins present in the database. Chemical modification of lysine, tyrosine, histidine, arginine, aspartic acid, and glutamic acid residues did not inhibit the hemagglutinating activity. However, the modification of tryptophan residues using N-bromosuccinimide showed the loss of hemagglutinating activity. Additionally, the mapping of tryptophan residues was performed to determine the extent and number of residues modified, which revealed that six residues per molecule were oxidized suggesting their accessibility. The retention of the lectin activity was seen when the modifications were performed in the presence of chitooligosaccharides due to protection of a tryptophan residue (W-102) in the protein. These studies taken together have led to the identification of a particular tryptophan residue (W-102) in the activity of the lectin. (c) 2015 IUBMB Life, 67(12):943-953, 2015

Resveratrol prevents inflammation-dependent hepatic melanoma metastasis by inhibiting the secretion and effects of interleukin-18

Background: Implantation and growth of metastatic cancer cells at distant organs is promoted by inflammation-dependent mechanisms. A hepatic melanoma metastasis model where a majority of metastases are generated via interleukin-18-dependent mechanisms was used to test whether anti-inflammatory properties of resveratrol can interfere with mechanisms of metastasis. Methods: Two experimental treatment schedules were used: 1) Mice received one daily oral dose of 1 mg/kg resveratrol after cancer cell injection and the metastasis number and volume were determined on day 12. 2) Mice received one daily oral dose of 1 mg/kg resveratrol along the 5 days prior to the injection of cancer cells and both interleukin-18 (IL-18) concentration in the hepatic blood and microvascular retention of luciferase-transfected B16M cells were determined on the 18(th) hour. In vitro, primary cultured hepatic sinusoidal endothelial cells were treated with B16M-conditioned medium to mimic their in vivo activation by tumor-derived factors and the effect of resveratrol on IL-18 secretion, on vascular cell adhesion molecule-1 (VCAM-1) expression and on tumor cell adhesion were studied. The effect of resveratrol on melanoma cell activation by IL-18 was also studied. Results: Resveratrol remarkably inhibited hepatic retention and metastatic growth of melanoma cells by 50% and 75%, respectively. The mechanism involved IL-18 blockade at three levels: First, resveratrol prevented IL-18 augmentation in the blood of melanoma cell-infiltrated livers. Second, resveratrol inhibited IL-18-dependent expression of VCAM-1 by tumor-activated hepatic sinusoidal endothelium, preventing melanoma cell adhesion to the microvasculature. Third, resveratrol inhibited adhesion-and proliferation-stimulating effects of IL-18 on metastatic melanoma cells through hydrogen peroxide-dependent nuclear factor-kappaB translocation blockade on these cells. Conclusions: These results demonstrate multiple sites for therapeutic intervention using resveratrol within the prometastatic microenvironment generated by tumor-induced hepatic IL-18, and suggest a remarkable effect of resveratrol in the prevention of inflammation-dependent melanoma metastasis in the liver.

Mechanism and applications of the photochemistry of Bis(η^5-cyclopentadienyl)titanacyclobutanes

The photochemically induced reductive elimination of cyclopropanes from bis(η⁵-cyclopentadienyl)titanacyclobutanes has been examined. Stereochemical labelling studies indicate that the cyclopropane is initially formed in a 6±1:1, ratio favoring retention of stereochemistry. The starting titanacyclobutane is isomerized during the course of the reaction. The isomerization of the starting material results from metal-carbon bond homolysis to yield a 1,4-biradical, which can either close to give the starting material or generate cyclopropane. The 1,4-biradical can be observed through a cyclopropyl carbinyl rearrangement employing 2-bis(η⁵- cyclopentadienyl)titana-5,5-dimethylbicyclo[2.1.0]pentane, to give the titanium alkylidene, 1-bis(η⁵-cyclopentadienyl)titana-3,3-dimethyl-1,4- pentadiene, which can be observed directly by NMR at low temperature.

The oxidation of titanacyclobutanes by chemical and electrochemical methods also yields cyclopropanes. Reduction of the metal center does not yield cyclopropanes. Depending on the oxidant, stereochemically labelled titanacyclobutanes yield cyclopropanes that are between 7:1 and 100:1 retention:isomerization. The fragmentation reaction resembles the photochemically induced reductive elimination. Both result from formal oxidation of a metal-carbon bond, which then results in very rapid formation of cyclopropane.

The titanocene generated photochemically reacts with a variety of substrates even at low temperature. Titanocene can be generated in a glass at 77 K. The titanocene can be trapped in noncoordinating solvents in high yield with bulky internal acetylenes to give monoacetylene adducts of titanocene. Less bulky acetylenes give the titanacyclopentadienes. The titanocene can be trapped with olefins to give less stable adducts, which appear by NMR analysis to be intermediate in structure between a titanacyclopropane and an η² olefin adduct of titanocene. Reaction of titanocene with butadiene gives a stable product, which appears to be the s-trans butadiene adduct of titanocene. It does not isomerize on heating. Titanocene reacts with epoxides to give titanocene-µ-oxo polymer and olefin. Stereochemically labelled epoxides and episulfides yield isomerized olefin upon deoxygenation by titanocene. The observations are rationalized as a result of a 1,4-biradical formed by stepwise insertion of titanocene into a carbon-oxygen bond.