New insights into the molecular structure of kaolinite–methanol intercalation complexes

A series of kaolinite–methanol complexes with different basal spacings were synthesized using guest displacement reactions of the intercalation precursors kaolinite–N-methyformamide (Kaol–NMF), kaolinite–urea (Kaol–U), or kaolinite–dimethylsulfoxide (Kaol–DMSO), with methanol (Me). The interaction of methanol with kaolinite was examined using X-ray diffraction (XRD), infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Kaolinite (Kaol) initially intercalated with N-methyformamide (NMF), urea (U), or dimethylsulfoxide (DMSO) before subsequent reaction with Me formed final kaolinite–methanol (Kaol–Me) complexes characterized by basal spacing ranging between 8.6 Å and 9.6 Å, depending on the pre-intercalated reagent. Based on a comparative analysis of the three Kaol–Me displacement intercalation complexes, three types of Me intercalation products were suggested to have been present in the interlayer space of Kaol: (1) molecules grafted onto a kaolinite octahedral sheet in the form of a methoxy group (Al-O-C bond); (2) mobile Me and/or water molecules kept in the interlayer space via hydrogen bonds that could be partially removed during drying; and (3) a mixture of types 1 and 2, with the methoxy group (Al-O-C bond) grafted onto the Kaol sheet and mobile Me and/or water molecules coexisted in the system after the displacement reaction by Me. Various structural models that reflected four possible complexes of Kaol–Me were constructed for use in a complimentary computational study. Results from the calculation of the methanol kaolinite interaction indicate that the hydroxyl oxygen atom of methanol plays the dominant role in the stabilization and localization of the molecule intercalated in the interlayer space, and that water existing in the intercalated Kaol layer is inevitable.

Identifying relationships between symptom clusters and quality of life in adults with chronic mixed venous and arterial leg ulcers

The objective of this study was to identify symptom clusters and their effect on quality of life (QOL) of adults with chronic leg ulcers of mixed venous and arterial aetiology. A secondary analysis of data from four existing prospective longitudinal studies conducted by a wound healing research group in Australia was undertaken. A total of 110 patients who met the inclusion criteria were selected for this study. Exploratory factor analysis (EFA) was used to identify symptom clusters and correlational analyses to examine relationships between the identified symptom clusters and QOL. The EFA identified two distinct symptom clusters: a 'systemic symptom cluster' consisting of pain, fatigue and depressive symptoms; and a 'localised-leg symptom cluster' including pain, fatigue, oedema, lower limb inflammation and exudate. Physical QOL correlated significantly with the systemic symptom cluster (r = -0·055, P < 0·0001) and the localised-leg symptom cluster (r = -0·054, P < 0·0001), whereas mental QOL was associated only with the systemic symptom cluster (r = -0·038, P = 0·01). The results suggest that appropriate intervention strategies targeting specific symptom clusters should be developed. Targeting patients with symptom clusters is particularly important because they are at high risk and the most vulnerable for reduced QOL.

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.

Typologies and touchpoints: Designing multi-channel digital strategies

Purpose This study aims to gain a clearer understanding of digital channel design. The emergence of new technologies has revolutionised the way companies interact and engage with customers. The driver for this research was the suggestion that practitioners feel they do not possess the skills to understand and exploit new digital channel opportunities. To gain a clearer understanding of digital channel design, this paper addresses the research question: What digital channels do companies from a wide range of industries and sectors use? Design/methodology/approach A content analysis of 100 international companies was conducted with multiple data sources to form a typology of digital “touchpoints”. The appropriateness of a digital channel typology for this study was for developing rigorous and useful concepts for clarifying and refining the meaning of digital channels. Findings This study identifies what digital channels companies globally currently employ and explores the related needs across industries. A total of 34 digital touchpoints and 4 typologies of digital channels were identified across 16 industries. This research helps to identify the relationship between digital channels and enabling the connections with industry. Research limitations/implications The findings contribute to the growing research area of digital channels. The typology of digital channels is a useful starting point for developing a systematic, theory-based study for enabling the development of broader, comprehensive theories of digital channels. Practical implications Typologies and touchpoints are outlined in relation to industry, company objectives and customer needs to allow businesses to seize opportunities and optimise performance through individual touchpoints. A digital channel model as a key outcome of this research guides practitioners on what touchpoint to implement through an interrelated understanding of industry, company and customer needs. Originality/value This is the first paper to explore a range of industries in relation to their use of digital channels using a unique content analysis. Contributions include clarifying and refining digital channel meaning; identifying and refining the hierarchical relations among digital channels(typologies); and establishing typology and industry relationship model.

Effect of constitutive material models on seismic response of two-story reinforced concrete frame

This paper focuses on the finite element (FE) response sensitivity and reliability analyses considering smooth constitutive material models. A reinforced concrete frame is modeled for FE sensitivity analysis followed by direct differentiation method under both static and dynamic load cases. Later, the reliability analysis is performed to predict the seismic behavior of the frame. Displacement sensitivity discontinuities are observed along the pseudo-time axis using non-smooth concrete and reinforcing steel model under quasi-static loading. However, the smooth materials show continuity in response sensitivity at elastic to plastic transition points. The normalized sensitivity results are also used to measure the relative importance of the material parameters on the structural responses. In FE reliability analysis, the influence of smoothness behavior of reinforcing steel is carefully noticed. More efficient and reasonable reliability estimation can be achieved by using smooth material model compare with bilinear material constitutive model.

The prevalence of anisometropia, amblyopia and strabismus in schoolchildren of Shiraz, Iran

PURPOSE To determine the prevalence of amblyopia, anisometropia, and strabismus in schoolchildren of Shiraz, Iran. MATERIALS AND METHODS A random cluster sampling was used in a cross-sectional study on schoolchildren in Shiraz. Cycloplegic refraction was performed in elementary and middle school children and high school students had non-cylcoplegic refraction. Uncorrected visual acuity (UCVA) and best corrected visual acuity (BCVA) were recorded for each participant. Anisometropia was defined as spherical equivalent (SE) refraction difference 1.00D or more between two eyes. Amblyopia was distinguished as a reduction of BCVA to 20/30 or less in one eye or 2-line interocular optotype acuity differences in the absence of pathological causes. Cover test was performed for investigating of strabismus. RESULTS Mean age of 2638 schoolchildren was 12.5 years (response rate = 86.06%). Prevalence of anisometropia was 2.31% (95% confidence interval [CI], 1.45 to 3.16). 2.29% of schoolchildren (95% CI, 1.46 to 3.14) were amblyopic. The prevalence of amblyopia in boys and girls was 2.32% and 2.26%, respectively (p = 0.945). Anisometropic amblyopia was found in 58.1% of the amblyopic subjects. The strabismus prevalence was 2.02% (95% CI, 1.18 to 2.85). The prevalence of exotropia and esotropia was 1.30% and 0.59%, respectively. CONCLUSIONS Results of this study showed that the prevalence of anisometropia, amblyopia, and strabismus are in the mid range. The etiology of amblyopia was often refractive, mostly astigmatic, and non-strabismic. Exotropia prevalence increased with age and was the most common strabismus type.

Futile treatment in hospital: Doctors’ intergroup language

Treatment that will not provide significant net benefit at the end of a person’s life (called futile treatment) is considered by many people to represent a major problem in the health sector, as it can waste resources and raise significant ethical issues. Medical treatment at the end of life involves a complex negotiation that implicates intergroup communication between health professionals, patients, and families, as well as between groups of health professionals. This study, framed by intergroup language theory, analyzed data from a larger project on futile treatment, in order to examine the intergroup language associated with futile treatment. Hospital doctors (N = 96) were interviewed about their understanding of treatment given to adult patients at the end of life that they considered futile. We conducted a discourse analysis on doctors’ descriptions of futile treatment provided by themselves and their in-group and out-group colleagues. Results pointed to an intergroup context, with patients, families, and colleagues as out-groups. In their descriptions, doctors justified their own decisions using the language of logic, ethics, and respect. Patients and families, however, were characterized in terms of wishing and wanting, as were outgroup colleagues. In addition, out-group doctors were described in strongly negative intergroup language.

Raman and infrared spectroscopic characterization of the silicate mineral lamprophyllite

The mineral lamprophyllite is fundamentally a silicate based upon tetrahedral siloxane units with extensive substitution in the formula. Lamprophyllite is a complex group of sorosilicates with general chemical formula given as A2B4C2Si2O7(X)4, where the site A can be occupied by strontium, barium, sodium, and potassium; the B site is occupied by sodium, titanium, iron, manganese, magnesium, and calcium. The site C is mainly occupied by titanium or ferric iron and X includes the anions fluoride, hydroxyl, and oxide. Chemical composition shows a homogeneous phase, composed of Si, Na, Ti, and Fe. This complexity of formula is reflected in the complexity of both the Raman and infrared spectra. The Raman spectrum is characterized by intense bands at 918 and 940 cm−1. Other intense Raman bands are found at 576, 671, and 707 cm−1. These bands are assigned to the stretching and bending modes of the tetrahedral siloxane units.

Physiological and biomechanical responses to walking underwater on a non-motorised treadmill: Effects of different exercise intensities and depths in middle-aged healthy women

Non-motorised underwater treadmills are commonly used in fitness activities. However, no studies have examined physiological and biomechanical responses of walking on non-motorised treadmills at different intensities and depths. Fifteen middle-aged healthy women underwent two underwater walking tests at two different depths, immersed either up to the xiphoid process (deep water) or the iliac crest (shallow water), at 100, 110, 120, 130 step-per-minute (spm). Oxygen consumption (VO2), heart rate (HR), blood lactate concentration, perceived exertion and step length were determined. Compared to deep water, walking in shallow water exhibited, at all intensities, significantly higher VO2 (+13.5%, on average) and HR (+8.1%, on average) responses. Water depth did not influence lactate concentration, whereas perceived exertion was higher in shallow compared to deep water, solely at 120 (+40%) and 130 (+39.4%) spm. Average step length was reduced as the intensity increased (from 100 to 130 spm), irrespective of water depth. Expressed as a percentage of maximum, average VO2 and HR were: 64–76% of peak VO2 and 71–90% of maximum HR, respectively at both water depths. Accordingly, this form of exercise can be included in the “vigorous” range of exercise intensity, at any of the step frequencies used in this study.

Development of brain structural connectivity between ages 12 and 30: A 4-Tesla diffusion imaging study in 439 adolescents and adults

Understanding how the brain matures in healthy individuals is critical for evaluating deviations from normal development in psychiatric and neurodevelopmental disorders. The brain's anatomical networks are profoundly re-modeled between childhood and adulthood, and diffusion tractography offers unprecedented power to reconstruct these networks and neural pathways in vivo. Here we tracked changes in structural connectivity and network efficiency in 439 right-handed individuals aged 12 to 30 (211 female/126 male adults, mean age=23.6, SD=2.19; 31 female/24 male 12 year olds, mean age=12.3, SD=0.18; and 25 female/22 male 16 year olds, mean age=16.2, SD=0.37). All participants were scanned with high angular resolution diffusion imaging (HARDI) at 4 T. After we performed whole brain tractography, 70 cortical gyral-based regions of interest were extracted from each participant's co-registered anatomical scans. The proportion of fiber connections between all pairs of cortical regions, or nodes, was found to create symmetric fiber density matrices, reflecting the structural brain network. From those 70 × 70 matrices we computed graph theory metrics characterizing structural connectivity. Several key global and nodal metrics changed across development, showing increased network integration, with some connections pruned and others strengthened. The increases and decreases in fiber density, however, were not distributed proportionally across the brain. The frontal cortex had a disproportionate number of decreases in fiber density while the temporal cortex had a disproportionate number of increases in fiber density. This large-scale analysis of the developing structural connectome offers a foundation to develop statistical criteria for aberrant brain connectivity as the human brain matures.

Genome-wide scan of healthy human connectome discovers SPON1 gene variant influencing dementia severity

Aberrant connectivity is implicated in many neurological and psychiatric disorders, including Alzheimer's disease and schizophrenia. However, other than a few disease-associated candidate genes, we know little about the degree to which genetics play a role in the brain networks; we know even less about specific genes that influence brain connections. Twin and family-based studies can generate estimates of overall genetic influences on a trait, but genome-wide association scans (GWASs) can screen the genome for specific variants influencing the brain or risk for disease. To identify the heritability of various brain connections, we scanned healthy young adult twins with high-field, highangular resolution diffusion MRI. We adapted GWASs to screen the brain's connectivity pattern, allowing us to discover genetic variants that affect the human brain's wiring. The association of connectivity with the SPON1 variant at rs2618516 on chromosome 11 (11p15.2) reached connectome-wide, genome-wide significance after stringent statistical corrections were enforced, and it was replicated in an independent subsample. rs2618516 was shown to affect brain structure in an elderly population with varying degrees of dementia. Older people who carried the connectivity variant had significantly milder clinical dementia scores and lower risk of Alzheimer's disease. As a posthoc analysis, we conducted GWASs on several organizational and topological network measures derived from the matrices to discover variants in and around genes associated with autism (MACROD2), development (NEDD4), and mental retardation (UBE2A) significantly associated with connectivity. Connectome-wide, genome-wide screening offers substantial promise to discover genes affecting brain connectivity and risk for brain diseases.

Multiple sulfur isotope analyses support a magmatic model for the volcanogenic massive sulfide deposits of the Teutonic Bore volcanic complex, Yilgarn Craton, Western Australia

We report sensitive high mass resolution ion microprobe, stable isotopes (SHRIMP SI) multiple sulfur isotope analyses (32S, 33S, 34S) to constrain the sources of sulfur in three Archean VMS deposits—Teutonic Bore, Bentley, and Jaguar—from the Teutonic Bore volcanic complex of the Yilgarn Craton, Western Australia, together with sedimentary pyrites from associated black shales and interpillow pyrites. The pyrites from VMS mineralization are dominated by mantle sulfur but include a small amount of slightly negative mass-independent fractionation (MIF) anomalies, whereas sulfur from the pyrites in the sedimentary rocks has pronounced positive MIF, with ∆33S values that lie between 0.19 and 6.20‰ (with one outlier at −1.62‰). The wall rocks to the mineralization include sedimentary rocks that have contributed no detectable positive MIF sulfur to the VMS deposits, which is difficult to reconcile with the leaching model for the formation of these deposits. The sulfur isotope data are best explained by mixing between sulfur derived from a magmatic-hydrothermal fluid and seawater sulfur as represented by the interpillow pyrites. The massive sulfide lens pyrites have a weighted mean ∆33S value of −0.27 ± 0.05‰ (MSWD = 1.6) nearly identical with −0.31 ± 0.08‰ (MSWD = 2.4) for pyrites from the stringer zone, which requires mixing to have occurred below the sea floor. We employed a two-component mixing model to estimate the contribution of seawater sulfur to the total sulfur budget of the two Teutonic Bore volcanic complex VMS deposits. The results are 15 to 18% for both Teutonic Bore and Bentley, much higher than the 3% obtained by Jamieson et al. (2013) for the giant Kidd Creek deposit. Similar calculations, carried out for other Neoarchean VMS deposits give value between 2% and 30%, which are similar to modern hydrothermal VMS deposits. We suggest that multiple sulfur isotope analyses may be used to predict the size of Archean VMS deposits and to provide a vector to ore deposit but further studies are needed to test these suggestions.

Transforming beyond self: fluidity of parent identity in family decision-making

When a household welcomes a new infant a transformation occurs whereby household routines, values and decisions change. This research explores how decision-making is influenced by fluctuating identity subjectivities. We explore longitudinally, using a family identity framework, how the transitioning between self, couple and family self-identities influences the decisions made regarding social issues, in this case infant feeding. Results indicate that decision-making during a period of transformation is not straightforward, relying on a multiplicity of identities that are constantly renegotiated and dependent on other influences. Decisions made conform to the identity-construct-of-the-moment, but are fluid and subject to change, such that pinpointing causal pathways is inappropriate. Implications for influencing the consumption of social behaviors for consumer researchers are one size does not fit all and require an in-depth understanding of the fluidity of decision-making. Consequently, social marketing strategies need to be tailored to constructed identities and flexible across time to remain influential.

Super DNAging - New insights into DNA integrity, genome stability and telomeres in the oldest old

Reductions in DNA integrity, genome stability, and telomere length are strongly associated with the aging process, age-related diseases as well as the age-related loss of muscle mass. However, in people reaching an age far beyond their statistical life expectancy the prevalence of diseases, such as cancer, cardiovascular disease, diabetes or dementia, is much lower compared to “averagely” aged humans. These inverse observations in nonagenarians (90–99 years), centenarians (100–109 years) and super-centenarians (110 years and older) require a closer look into dynamics underlying DNA damage within the oldest old of our society. Available data indicate improved DNA repair and antioxidant defense mechanisms in “super old” humans, which are comparable with much younger cohorts. Partly as a result of these enhanced endogenous repair and protective mechanisms, the oldest old humans appear to cope better with risk factors for DNA damage over their lifetime compared to subjects whose lifespan coincides with the statistical life expectancy. This model is supported by study results demonstrating superior chromosomal stability, telomere dynamics and DNA integrity in “successful agers”. There is also compelling evidence suggesting that life-style related factors including regular physical activity, a well-balanced diet and minimized psycho-social stress can reduce DNA damage and improve chromosomal stability. The most conclusive picture that emerges from reviewing the literature is that reaching “super old” age appears to be primarily determined by hereditary/genetic factors, while a healthy lifestyle additionally contributes to achieving the individual maximum lifespan in humans. More research is required in this rapidly growing population of super old people. In particular, there is need for more comprehensive investigations including short- and long-term lifestyle interventions as well as investigations focusing on the mechanisms causing DNA damage, mutations, and telomere shortening.

Association of variants at 1q32 and STAT3 with ankylosing spondylitis suggests genetic overlap with Crohn's disease

Ankylosing spondylitis (AS) is a common inflammatory arthritic condition. Overt inflammatory bowel disease (IBD) occurs in about 10% of AS patients, and in addition 70% of AS cases may have subclinical terminal ileitis. Spondyloarthritis is also common in IBD patients. We therefore tested Crohn's disease susceptibility genes for association with AS, aiming to identify pleiotropic genetic associations with both diseases. Genotyping was carried out using Sequenom and Applied Biosystems TaqMan and OpenArray technologies on 53 markers selected from 30 Crohn's disease associated genomic regions. We tested genotypes in a population of unrelated individual cases (n = 2,773) and controls (n = 2,215) of white European ancestry for association with AS. Statistical analysis was carried out using a Cochran-Armitage test for trend in PLINK. Strong association was detected at chr1q32 near KIF21B (rs11584383, P = 1.66 x 10-10, odds ratio (OR) = 0.74, 95% CI:0.68-0.82). Association with disease was also detected for 2 variants within STAT3 (rs6503695, P = 4.6×10-4. OR = 0.86 (95% CI:0.79-0.93); rs744166, P = 2.6×10-5, OR = 0.84 (95% CI:0.77-0.91)). Association was confirmed for IL23R (rs11465804, P = 1.2×10-5, OR = 0.65 (95% CI:0.54-0.79)), and further associations were detected for IL12B (rs10045431, P = 5.261025, OR = 0.83 (95% CI:0.76-0.91)), CDKAL1 (rs6908425, P = 1.1×10-4, OR = 0.82 (95% CI:0.74-0.91)), LRRK2/MUC19 (rs11175593, P = 9.9×10-5, OR = 1.92 (95% CI: 1.38-2.67)), and chr13q14 (rs3764147, P = 5.9×10-4, OR = 1.19 (95% CI: 1.08-1.31)). Excluding cases with clinical IBD did not significantly affect these findings. This study identifies chr1q32 and STAT3 as ankylosing spondylitis susceptibility loci. It also further confirms association for IL23R and detects suggestive association with another 4 loci. STAT3 is a key signaling molecule within the Th17 lymphocyte differentiation pathway and further enhances the case for a major role of this T-lymphocyte subset in ankylosing spondylitis. Finally these findings suggest common aetiopathogenic pathways for AS and Crohn's disease and further highlight the involvement of common risk variants across multiple diseases.