Synthesis and structural analysis of [alpha]-aminophosphonic acids and their phosphonate ester derivatives

The aims of this project fall into two main categories. The primary objective was the preparation and characterisation of novel [alpha]-aminophosphonic acids and their phosphonate ester derivatives. Compounds of these types are of interest because of their potential for biological activity, particularly in the area of agricultural chemistry. The second objective was to investigate the conformation of selected examples of these types of molecules in solution. This was achieved by considering the proton-proton and proton-phosphorus coupling constants. These coupling constants were obtained by the full analysis of the 1H NMR spectra. The strategy adopted for the preparation of the phosphonic acids started from the synthesis of imine precursors. The imines were prepared by condensing aminodiphenylmethane or [alpha]-methylbenzylamine with a wide variety of aldehydes and ketones, using very mild reaction conditions. The imine precursors were then reacted with diethyl (or dimethyl) phosphite to give diethyl (or dimethyl) 1-substituted-l-(diphenylmethylamino)methanephosphonates, which were isolated and characterised. The phosphonate esters prepared from the reactions of imines derived from [alpha]-methylbenzylamine were not isolated. A series of the phosphonate esters [diethyl 1-phenyl-l-(diphenylmethylamino)methanephosphonate, diethyl l-(l’-naphthyl)-l-(diphenylmethylamino)methanephosphonate and diethyl l-(1’-pyrenyl)-l-(diphenylmethylamino)methanephosphonate] were selected for full 1H NMR spectral analysis. The effects of the aromatic ring currents exerted by the extended aromatic substituents were investigated. The complex aromatic regions of the 1H NMR spectra were not analysed. The X-ray crystal structures of selected diethyl 1-substituted-1- (diphenylmethylamino)methanephosphonates, where the substituents are: phenyl, 1’-naphthyl, 9'-anthryl, I'-pyrenyl, 2'-pyrrolyl and piperonyl, were determined and are discussed. The phosphonate esters were subjected to acid-hydrolysis to yield the [alpha]-aminophosphonic acids, including l-N-phenylethylamino-l-(2'-thienyl)phosphonic acid which was prepared from the imine derived from [alpha]-methylbenzylamine. Full 1H NMR spectral analysis was carried out on [alpha]-aminopropanephosphonic acid at three different pH values. The results of these analyses are discussed and compared with the results of the NMR spectral analysis of [alpha]-aminopropanephosphinic acid

Carbon isotope ratioss of coccolith-associated polysaccharides of Emiliania huxleyi as a function of growth rate and CO2 concentration

The calcite plates, or coccoliths, of haptophyte algae including Emiliania huxleyi are formed in intracellular vesicles in association with water–soluble acidic polysaccharides. These coccolith–associated polysaccharides (CAPs) are involved in regulating coccolith formation and have been recovered from sediment samples dating back to ∼180 Ma. Paired measurements of the carbon isotopic compositions of CAPs and coccolith calcite have been proposed as a novel paleo–pCO2 barometer, but additional proxy validation and development are still required. Here we present culture results quantifying carbon isotopic offsets between CAPs and other cellular components: bulk organic biomass, alkenones, and calcite. E. huxleyi was grown in nitrate–limited chemostat experiments at growth rates (µ) of 0.20–0.62/d and carbon dioxide concentrations of 10.7–17.6 µmol/kg. We find that CAPs are isotopically enriched by 4.5–10.1‰ relative to bulk organic carbon, exhibiting smaller isotopic offsets at faster growth rates and lower CO2 concentrations. This variability suggests that CAPs record a complementary signature of past growth conditions with different sensitivity than alkenones or coccolith calcite. By measuring the isotopic compositions of all three molecules and minerals of self-consistent origin, the ratio µ/[CO2(aq)] may be reconstructed with fewer assumptions than current approaches

Impact of Personalization on Acquisition and Generalization of Script Training: A Preliminary Analysis

Eight individuals with chronic aphasia underwent intensive computer-based script training. Trained and untrained generalization scripts, matched for length and complexity, were developed. The two scripts shared personalized and non-personalized words/phrases. Training lasted three weeks. Script performance was probed periodically. For acquisition, the gain from baseline to post-treatment for both personalized and non-personalized words/phrases on the trained script was significant; the effect size of personalization over non-personalization was moderate. For generalization, the gain for both personalized and non-personalized items was also significant, but the effect size of personalization over non-personalization was small. Limitations of the study are discussed

Religious and spiritual issues in clinical and counselling psychology masters training programmes in South African universities : an exploratory study.

Thesis (M.A.)-University of KwaZulu-Natal, 2007.Religion and spirituality are universal concepts which provide significant platforms of meaning for many people (Pargament, 1999). However, traditional psychology training programs have typically omitted these issues (Brawer, Handal, Fabricatore, Roberts and Wadja-Johnston, 2002; Shafranske, 2001), thus neglecting an important dimension of human experience. The present study involved sending a survey questionnaire to all lecturers, coordinators and directors involved in psychology masters programmes within South Africa. This study explores the extent to which religious and spiritual issues are currently included in masters programmes, the perceptions of those involved regarding religious and spiritual issues, and possible ways of integrating these issues within the existing program. Within an integrative framework, results are analysed descriptively, using content analysis for the qualitative responses. Current inclusion of religious and spiritual issues within psychology training programs is varied between modules and universities, and the perceptions of those involved regarding inclusion is ambivalently in favour. Integrating religious and spiritual issues into existing modules is generally favoured

Exploring how social workers experience and cope with public perception of their profession

The public's perception of the social work profession is a rarely considered perspective and yet a topic that is a concern to front line professionals. This paper explores how social workers experience and attempt to cope with public perception of their profession. It highlights the impact of these concerns on social workers' personal experiences and professional practice. Using semi-structured interviews with sixteen UK social workers, from local authorities and private organisations, we explore the experiences of this group. Thematic analysis of the data identified four concerns: the experience of public perception, drivers of public perception, coping with public perception, and mechanisms to raise the professions profile. Examining public perception through the eyes of social workers provides valuable insights into the lived experiences of these professionals, and offers practical implications at both the micro and macro levels. It reveals two key ways in which the profession can begin to address the prevailing negative perception considered to be emanating from the public: through developing a more co-operative relationship with external sources of public perception (e.g. government and the media) and by engaging in more pro-active self-promotion of the service

Multipar-T: Multiparty-Transformer for Capturing Contingent Behaviors in Group Conversations

As we move closer to real-world AI systems, AI agents must be able to deal with multiparty (group) conversations. Recognizing and interpreting multiparty behaviors is challenging, as the system must recognize individual behavioral cues, deal with the complexity of multiple streams of data from multiple people, and recognize the subtle contingent social exchanges that take place amongst group members. To tackle this challenge, we propose the Multiparty-Transformer (Multipar-T), a transformer model for multiparty behavior modeling. The core component of our proposed approach is the Crossperson Attention, which is specifically designed to detect contingent behavior between pairs of people. We verify the effectiveness of Multipar-T on a publicly available video-based group engagement detection benchmark, where it outperforms state-of-the-art approaches in average F-1 scores by 5.2% and individual class F-1 scores by up to 10.0%. Through qualitative analysis, we show that our Crossperson Attention module is able to discover contingent behavior.Comment: 7 pages, 4 figures, IJCA

Measuring Engagement in Robot-Assisted Autism Therapy: A Cross-Cultural Study

During occupational therapy for children with autism, it is often necessary to elicit and maintain engagement for the children to benefit from the session. Recently, social robots have been used for this; however, existing robots lack the ability to autonomously recognize the children’s level of engagement, which is necessary when choosing an optimal interaction strategy. Progress in automated engagement reading has been impeded in part due to a lack of studies on child-robot engagement in autism therapy. While it is well known that there are large individual differences in autism, little is known about how these vary across cultures. To this end, we analyzed the engagement of children (age 3–13) from two different cultural backgrounds: Asia (Japan, n = 17) and Eastern Europe (Serbia, n = 19). The children participated in a 25 min therapy session during which we studied the relationship between the children’s behavioral engagement (task-driven) and different facets of affective engagement (valence and arousal). Although our results indicate that there are statistically significant differences in engagement displays in the two groups, it is difficult to make any causal claims about these differences due to the large variation in age and behavioral severity of the children in the study. However, our exploratory analysis reveals important associations between target engagement and perceived levels of valence and arousal, indicating that these can be used as a proxy for the children’s engagement during the therapy. We provide suggestions on how this can be leveraged to optimize social robots for autism therapy, while taking into account cultural differences.MEXT Grant-in-Aid for Young Scientists B (grant no. 16763279)Chubu University Grant I (grant no. 27IS04I (Japan))European Union. HORIZON 2020 (grant agreement no. 701236 (ENGAGEME))European Commission. Framework Programme for Research and Innovation. Marie Sklodowska-Curie Actions (Individual Fellowship)European Commission. Framework Programme for Research and Innovation. Marie Sklodowska-Curie Actions (grant agreement no. 688835 (DE-ENIGMA)

Reply to Morel : cadmium as a micronutrient and macrotoxin in the oceans

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of America 110 (2013): E1878, doi:10.1073/pnas.1305068110.We thank François Morel for his interest in our study. Morel states that our conclusions are based on the approximate match between the Cd-isotope composition of cultured bacteria and the fractionation of Cd isotopes seen in seawater (1). This match is only a minor component of our argument, and we welcome the opportunity to reiterate our case

Multi-task multiple kernel machines for personalized pain recognition from functional near-infrared spectroscopy brain signals

Currently there is no validated objective measure of pain. Recent neuroimaging studies have explored the feasibility of using functional near-infrared spectroscopy (fNIRS) to measure alterations in brain function in evoked and ongoing pain. In this study, we applied multi-task machine learning methods to derive a practical algorithm for pain detection derived from fNIRS signals in healthy volunteers exposed to a painful stimulus. Especially, we employed multi-task multiple kernel learning to account for the inter-subject variability in pain response. Our results support the use of fNIRS and machine learning techniques in developing objective pain detection, and also highlight the importance of adopting personalized analysis in the process.Comment: International Conference on Pattern Recognition (ICPR