Vibrational spectroscopic characterization of the phosphate mineral kulanite Ba(Fe2+,Mn2+,Mg)2(Al,Fe3+)2(PO4)3(OH)3

The mineral kulanite BaFe2Al2(PO4)3(OH)3, a barium iron aluminum phosphate, has been studied by using a combination of electron microscopy and vibrational spectroscopy. Scanning electron microscopy with EDX shows the mineral is homogenous with no other phases present. The Raman spectrum is dominated by an intense band at 1022 cm−1 assigned to the PO43-ν1 symmetric stretching mode. Low intensity Raman bands at 1076, 1110, 1146, 1182 cm−1 are attributed to the PO43-ν3 antisymmetric stretching vibrations. The infrared spectrum shows a complex spectral profile with overlapping bands. Multiple phosphate bending vibrations supports the concept of a reduction in symmetry of the phosphate anion. Raman spectrum at 3211, 3513 and 3533 cm−1 are assigned to the stretching vibrations of the OH units. Vibrational spectroscopy enables aspects on the molecular structure of kulanite to be assessed.

Synergism between Wnt3a and heparin enhances osteogenesis via a phosphoinositide 3-kinase/Akt/RUNX2 pathway

A new strategy has emerged to improve healing of bone defects using exogenous glycosaminoglycans by increasing the effectiveness of bone-anabolic growth factors. Wnt ligands play an important role in bone formation. However, their functional interactions with heparan sulfate/heparin have only been investigated in non-osseous tissues. Our study now shows that the osteogenic activity of Wnt3a is cooperatively stimulated through physical interactions with exogenous heparin. N-Sulfation and to a lesser extent O-sulfation of heparin contribute to the physical binding and optimal co-stimulation of Wnt3a. Wnt3a-heparin signaling synergistically increases osteoblast differentiation with minimal effects on cell proliferation. Thus, heparin selectively reduces the effective dose of Wnt3a needed to elicit osteogenic, but not mitogenic responses. Mechanistically, Wnt3a-heparin signaling strongly activates the phosphoinositide 3-kinase/Akt pathway and requires the bone-related transcription factor RUNX2 to stimulate alkaline phosphatase activity, which parallels canonical beta-catenin signaling. Collectively, our findings establish the osteo-inductive potential of a heparin-mediated Wnt3a-phosphoinositide 3-kinase/Akt-RUNX2 signaling network and suggest that heparan sulfate supplementation may selectively reduce the therapeutic doses of peptide factors required to promote bone formation.

Vibrational spectroscopic study of the sulphate mineral glaucocerinite (Zn,Cu)10Al6(SO4)3(OH)32⋅18H2O – a natural layered double hydroxide

We have studied the molecular structure of the mineral glaucocerinite (Zn,Cu)5Al3(SO4)1.5(OH)16�9(H2O) using a combination of Raman and infrared spectroscopy. The mineral is one of the hydrotalcite supergroup of natural layered double hydroxides. The Raman spectrum is characterised by an intense Raman band at 982 cm�1 with a low intensity band at 1083 cm�1. These bands are attributed to the sulphate symmetric and antisymmetric stretching mode. The infrared spectrum is quite broad with a peak at 1020 cm�1. A series of Raman bands at 546, 584, 602, 625 and 651 cm�1 are assigned to the m4 (SO4)2� bending modes. The observation of multiple bands provides evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 762 cm�1 is attributed to a hydroxyl deformation mode associated with AlOH units. Vibrational spectroscopy enables aspects of the molecular structure of glaucocerinite to be determined.

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

3,6-Di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione and bithiophene copolymer with rather disordered chain orientation showing high mobility in organic thin film transistors

Pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione or diketopyrrolopyrrole (DPP) is a useful electron-withdrawing fused aromatic moiety for the preparation of donor-acceptor polymers as active semiconductors for organic electronics. This study uses a DPP-furan-containing building block, 3,6-di(furan-2-yl)pyrrolo[3,4- c]pyrrole-1,4(2H,5H)-dione (DBF), to couple with a 2,2′-bithiophene unit, forming a new donor-acceptor copolymer, PDBFBT. Compared to its structural analogue, 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBT), DBF is found to cause blue shifts of the absorption spectra both in solution and in thin films and a slight reduction of the highest occupied molecular orbital (HOMO) energy level of the resulting PDBFBT. Despite the fact that its thin films are less crystalline and have a rather disordered chain orientation in the crystalline domains, PDBFBT shows very high hole mobility up to 1.54 cm 2 V-1 s-1 in bottom-gate, top-contact organic thin film transistors.

Molecular analysis of type 3 fimbrial genes from Escherichia coli, Klebsiella and Citrobacter species

Background Catheter-associated urinary tract infection (CAUTI) is the most common nosocomial infection in the United States and is caused by a range of uropathogens. Biofilm formation by uropathogens that cause CAUTI is often mediated by cell surface structures such as fimbriae. In this study, we characterised the genes encoding type 3 fimbriae from CAUTI strains of Escherichia coli, Klebsiella pneumoniae, Klebsiella oxytoca, Citrobacter koseri and Citrobacter freundii. Results Phylogenetic analysis of the type 3 fimbrial genes (mrkABCD) from 39 strains revealed they clustered into five distinct clades (A-E) ranging from one to twenty-three members. The majority of sequences grouped in clade A, which was represented by the mrk gene cluster from the genome sequenced K. pneumoniae MGH78578. The E. coli and K. pneumoniae mrkABCD gene sequences clustered together in two distinct clades, supporting previous evidence for the occurrence of inter-genera lateral gene transfer. All of the strains examined caused type 3 fimbriae mediated agglutination of tannic acid treated human erythrocytes despite sequence variation in the mrkD-encoding adhesin gene. Type 3 fimbriae deletion mutants were constructed in 13 representative strains and were used to demonstrate a direct role for type 3 fimbriae in biofilm formation. Conclusions The expression of functional type 3 fimbriae is common to many Gram-negative pathogens that cause CAUTI and is strongly associated with biofilm growth. Our data provides additional evidence for the spread of type 3 fimbrial genes by lateral gene transfer. Further work is now required to substantiate the clade structure reported here by examining more strains as well as other bacterial genera that make type 3 fimbriae and cause CAUTI.

Vascular endothelial growth factor receptor-3 directly interacts with phosphatidylinositol 3-kinase to regulate lymphangiogenesis

Background Dysfunctional lymphatic vessel formation has been implicated in a number of pathological conditions including cancer metastasis, lymphedema, and impaired wound healing. The vascular endothelial growth factor (VEGF) family is a major regulator of lymphatic endothelial cell (LEC) function and lymphangiogenesis. Indeed, dissemination of malignant cells into the regional lymph nodes, a common occurrence in many cancers, is stimulated by VEGF family members. This effect is generally considered to be mediated via VEGFR-2 and VEGFR-3. However, the role of specific receptors and their downstream signaling pathways is not well understood. Methods and Results Here we delineate the VEGF-C/VEGF receptor (VEGFR)-3 signaling pathway in LECs and show that VEGF-C induces activation of PI3K/Akt and MEK/Erk. Furthermore, activation of PI3K/Akt by VEGF-C/VEGFR-3 resulted in phosphorylation of P70S6K, eNOS, PLCc1, and Erk1/2. Importantly, a direct interaction between PI3K and VEGFR-3 in LECs was demonstrated both in vitro and in clinical cancer specimens. This interaction was strongly associated with the presence of lymph node metastases in primary small cell carcinoma of the lung in clinical specimens. Blocking PI3K activity abolished VEGF-C-stimulated LEC tube formation and migration. Conclusions Our findings demonstrate that specific VEGFR-3 signaling pathways are activated in LECs by VEGF-C. The importance of PI3K in VEGF-C/VEGFR-3-mediated lymphangiogenesis provides a potential therapeutic target for the inhibition of lymphatic metastasis.

Acute injuries in track and field athletes: A 3-year observational study at the Penn Relays Carnival with epidemiology and medical coverage implications

Background Few studies have examined acute injuries in track and field in both elite and sub-elite athletes. Purpose To observe the absolute and relative rates of injury in track and field athletes across a wide range of competition levels and ages during three years of the Penn Relays Carnival to assist with future medical coverage planning and injury prevention strategies. Study design: Descriptive epidemiology study. Methods Over a 3-year period all injuries treated by the medical staff were recorded on a standardised injury report form. Absolute injury rates (absolute number of injuries) and relative injury rates (number of injuries per 1000 participants) were determined and odds ratios (OR) of injury rates were calculated between sexes, competition levels and events. Injuries were also broken down into major or minor medical or orthopedic injuries. Results Throughout the study period 48,473 competing athletes participated in the Penn Relays Carnival, and 436 injuries were sustained. For medical coverage purposes, the relative rate of injury subtypes was greatest for minor orthopedic injuries (5.71 injuries per 1000 participants), followed by minor medical injuries (3.42 injuries per 1000 participants), major medical injuries (0.69 injuries per 1000 participants) and major orthopedic injuries (0.18 injuries per 1000 participants). College/elite level athletes displayed the lowest relative injury rate (7.99 injuries per 1000 participants), which was significantly less than high school (9.87 injuries per 1000 participants) and masters level athletes (16.33 injuries per 1000 participants). Males displayed a greater likelihood of suffering a minor orthopedic injury compared to females (OR = 1.36, 95% CI = 1.06 to 1.75; χ2 = 5.73, p = 0.017) but were less likely to sustain a major medical injury (OR = 0.33, 95% CI = 0.15 to 0.75; χ2 = 7.75, p = 0.005). Of the three most heavily participated in events, the 4 x 400m relay displayed the greatest relative injury rate (13.6 injuries per 1000 participants) compared to the 4 x 100 and 4 x 200m relay. Conclusions Medical coverage teams for future large scale track and field events need to plan for at least two major orthopedic and seven major medical injuries per 1000 participants. Male track and field athletes, particularly masters level male athletes, are at greater risk of injury compared to other genders and competition levels.

Expert Opinion: Serious Concerns regarding Western Australian Planning Commission (WAPC) Draft Policy 3.7 “Planning for Bushfire Risk Management” and associated Guidelines (May 2014)

10 page document containing expert assessment of shortcomings of Western Australian State Planning Policy SPP3.7- Planning for Bushfire Risk Management. Document produced on behalf of QUT and submitted to and published by the WAPC as part of their public consultation process for their draft policy.

Crystal structures and hydrogen bonding in the anhydrous tryptaminium salts of the isomeric (2,4-dichlorophenoxy)acetic and (3,5-dichlorophenoxy)acetic acids

The anhydrous salts of 1H-indole-3-ethanamine (tryptamine) with isomeric (2,4-dichlorophenoxy)acetic acid (2,4-D) and (3,5-dichlorophenoxy)acetic (3,5-D), C10H13N2+ (C8H5Cl2O3)-, [(I) and (II), respectively] have been determined and their one-dimensional hydrogen-bonded polymeric structures are described. In the crystal of (I),the aminium H-atoms are involved in three separate inter-species N-H...O hydrogen-bonding interactions, two with carboxyl O-atom acceptors and the third in an asymmetric three-centre bidentate carboxyl O,O' chelate [graph set R2/1(4)]. The indole H-atom forms an N-H...O~carboxyl~ hydrogen bond, extending the chain structure along the b axial direction. In (II), two of the three aminium H-atoms are also involved in N-H...O(carboxyl) hydrogen bonds similar to (I) but with the third, a three-centre asymmetric interaction with carboxyl and phenoxy O-atoms is found [graph set R2/1(5)]. The chain polymeric extension is also along b. There are no pi--pi ring interactions in either of the structures. The aminium side chain conformations differ significantly between the two structures, reflecting the conformational ambivalence of the tryptaminium cation, as found also in the benzoate salts.

Substrate effects in the supramolecular assembly of 1,3,5-benzene tricarboxylic acid on graphite and graphene

The behavior of small molecules on a surface depends critically on both molecule–substrate and intermolecular interactions. We present here a detailed comparative investigation of 1,3,5-benzene tricarboxylic acid (trimesic acid, TMA) on two different surfaces: highly oriented pyrolytic graphite (HOPG) and single-layer graphene (SLG) grown on a polycrystalline Cu foil. On the basis of high-resolution scanning tunnelling microscopy (STM) images, we show that the epitaxy matrix for the hexagonal TMA chicken wire phase is identical on these two surfaces, and, using density functional theory (DFT) with a non-local van der Waals correlation contribution, we identify the most energetically favorable adsorption geometries. Simulated STM images based on these calculations suggest that the TMA lattice can stably adsorb on sites other than those identified to maximize binding interactions with the substrate. This is consistent with our net energy calculations that suggest that intermolecular interactions (TMA–TMA dimer bonding) are dominant over TMA–substrate interactions in stabilizing the system. STM images demonstrate the robustness of the TMA films on SLG, where the molecular network extends across the variable topography of the SLG substrates and remains intact after rinsing and drying the films. These results help to elucidate molecular behavior on SLG and suggest significant similarities between adsorption on HOPG and SLG.

Origins of Australian Football: Victoria's Early History. Volume 3: Covert 'Professionalism': The Power of the Wealthy Clubs 1886 to 1890

This volume continues the story of football in Marvellous Melbourne during the 1880s. At this time the VFA continued to expand as Melbourne’s boom continued apace. In 1886 Port Melbourne, Prahran, St Kilda, Footscray and South Williamstown joined the competition, and the Ballarat clubs Ballarat, Ballarat Imperial and South Ballarat were also contending for the VFA premiership. In 1886 matches were divided into four quarters, goal umpires waved two flags to announce a goal, and time clocks and bells were employed to mark the end of quarters. Victoria also played inter-colonial matches against New South Wales, Tasmania and South Australia. VFA secretary T.S. Marshall was at the forefront of fighting the game’s turn towards professionalism, but although it was illegal to pay players, the practice continued. The period 1886 to 1890 also set the stage for the eventual formation of the Victorian Football League, for by the end of the 1880s the Victorian Football Association had become in effect a two-tier competition. The most popular clubs in the VFA, South Melbourne, Geelong, Carlton and Essendon collected the lion’s share of the gate money, which they used to build their wealth and entrench their position as the dominant Victorian teams. The lower tier clubs had to make do with paltry gate money and season fixtures that advantaged the strong clubs. In these fixtures the strong clubs elected to play each other first to increase their gate money, and only deemed to play the poorer clubs at the start of the season. This led to an increasing divide between the VFA’s rich and poor, and by 1890 South Williamstown and Prahran merged with Williamstown and St Kilda respectively, University dropped out of senior ranks, and the Ballarat clubs were excluded from competing for the VFA premiership, which left 12 senior clubs until Collingwood’s emergence in 1892. At this time, no team was as powerful as South Melbourne, which experienced the greatest success in the club’s VFA and VFL history when it collected triple premiership crowns in 1888, 1889, and 1890. South Melbourne was a most ambitious club and spearheaded the move towards professionalism, although this could not be made public. The fine teams it produced at this time contained some of the greatest players of the era, such as Peter Burns, “Sonny” Elms and “Dinny” McKay, and it looked after players with health insurance, jobs, inter-colonial trips, and other incentives. Geelong’s premiership in 1886 was perhaps its greatest triumph, but this success was followed by a premiership drought that would last for 39 years. Carlton remained one of Victorian football’s power clubs, and after securing the premiership in 1887 continued to compete for top honours. As always, the game became ever more popular and world record crowds of over 30,000 attended matches between South Melbourne, Carlton, Geelong and Essendon.

The relationship between number of fruits, vegetables, and noncore foods tried at age 14 months and food preferences, dietary intake patterns, fussy eating behavior, and weight status at age 3.7 years

Objective We examined whether exposure to a greater number of fruits, vegetables, and noncore foods (ie, nutrient poor and high in saturated fats, added sugars, or added salt) at age 14 months was related to children’s preference for and intake of these foods as well as maternal-reported food fussiness and measured child weight status at age 3.7 years. Methods This study reports secondary analyses of longitudinal data from mothers and children (n=340) participating in the NOURISH randomized controlled trial. Exposure was quantified as the number of food items (n=55) tried by a child from specified lists at age 14 months. At age 3.7 years, food preferences, intake patterns, and fussiness (also at age 14 months) were assessed using maternal-completed, established questionnaires. Child weight and length/height were measured by study staff at both age points. Multivariable linear regression models were tested to predict food preferences, intake patterns, fussy eating, and body mass index z score at age 3.7 years adjusting for a range of maternal and child covariates. Results Having tried a greater number of vegetables, fruits, and noncore foods at age 14 months predicted corresponding preferences and higher intakes at age 3.7 years but did not predict child body mass index z score. Adjusting for fussiness at age 14 months, having tried more vegetables at age 14 months was associated with lower fussiness at age 3.7 years. Conclusions These prospective analyses support the hypothesis that early taste and texture experiences influence subsequent food preferences and acceptance. These findings indicate introduction to a variety of fruits and vegetables and limited noncore food exposure from an early age are important strategies to improve later diet quality.