Tailoring the composition of self-assembled Si1−xCx quantum dots : simulation of plasma/ion-related controls

Precise control of composition and internal structure is essential for a variety of novel technological applications which require highly tailored binary quantum dots (QDs) with predictable optoelectronic and mechanical properties. The delicate balancing act between incoming flux and substrate temperature required for the growth of compositionally graded (Si1-xC x; x varies throughout the internal structure), core-multishell (discrete shells of Si and C or combinations thereof) and selected composition (x set) QDs on low-temperature plasma/ion-flux-exposed Si(100) surfaces is investigated via a hybrid numerical simulation. Incident Si and C ions lead to localized substrate heating and a reduction in surface diffusion activation energy. It is shown that by incorporating ions in the influx, a steady-state composition is reached more quickly (for selected composition QDs) and the composition gradient of a Si1-xCx QD may be fine tuned; additionally (with other deposition conditions remaining the same), larger QDs are obtained on average. It is suggested that ionizing a portion of the influx is another way to control the average size of the QDs, and ultimately, their internal structure. Advantages that can be gained by utilizing plasma/ion-related controls to facilitate the growth of highly tailored, compositionally controlled quantum dots are discussed as well.

Enhancing students' self-concepts and related constructs: A critical longitudinal analysis capitalising on and combining promising enhancement techniques for educational settings

Enhancing children's self-concepts is widely accepted as a critical educational outcome of schooling and is postulated as a mediating variable that facilitates the attainment of other desired outcomes such as improved academic achievement. Despite considerable advances in self-concept research, there has been limited progress in devising teacher-administered enhancement interventions. This is unfortunate as teachers are crucial change agents during important developmental periods when self-concept is formed. The primary aim of the present investigation is to build on the promising features of previous self-concept enhancement studies by: (a) combining two exciting research directions developed by Burnett and Craven to develop a potentially powerful cognitive-based intervention; (b) incorporating recent developments in theory and measurement to ensure that the multidimensionality of self-concept is accounted for in the research design; (c) fully investigating the effects of a potentially strong cognitive intervention on reading, mathematics, school and learning self-concepts by using a large sample size and a sophisticated research design; (d) evaluating the effects of the intervention on affective and cognitive subcomponents of reading, mathematics, school and learning self-concepts over time to test for differential effects of the intervention; (e) modifying and extending current procedures to maximise the successful implementation of a teacher-mediated intervention in a naturalistic setting by incorporating sophisticated teacher training as suggested by Hattie (1992) and including an assessment of the efficacy of implementation; and (f) examining the durability of effects associated with the intervention.

Development of self-efficacy and expectancy measures for benzodiazepines

This study aimed to develop and assess the reliability and validity of a pair of self-report questionnaires to measure self-efficacy and expectancy associated with benzodiazepine use, the Benzodiazepine Refusal Self- Efficacy Questionnaire (BRSEQ) and the Benzodiazepine Expectancy Questionnaire (BEQ). Internal structure of the questionnaireswas established by principal component analysis (PCA) in a sample of 155 respondents, and verified by confirmatory factor analyses (CFA) in a second independent sample (n=139) using structural equation modeling. The PCA of the BRSEQ resulted in a 16-item, 4-factor scale, and the BEQ formed an 18-item, 2-factor scale. Both scales were internally reliable. CFA confirmed these internal structures and reduced the questionnaires to a 14-item self-efficacy scale and a 12-item expectancy scale. Lower self-efficacy and higher expectancy were moderately associated with higher scores on the SDS-B. The scales provide reliable measures for assessing benzodiazepine self-efficacy and expectancies. Future research will examine the utility of the scales in prospective prediction of benzodiazepine cessation.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

Gifted young adolescents : voices of self

Despite the challenges that giftedness can add to self-formation during early adolescence, gifted young adolescents seldom are asked about their lives outside of counselling and educational contexts. The study considers the complexities that face gifted young adolescents in the process of self-discovery and self-representation, thereby building a case for seeking their own viewpoints. A guiding assumption for the study was that gifted young adolescents may respond positively to the opportunity to share their own perspectives and their own versions of “who they are”. The theoretical underpinnings for this study drew from Dialogical Self Theory. The study resides within an interactive view of self as a dynamic construction rather than a static state, where “who we are” is formed in everyday exchanges with self and others. Self-making as a process among gifted young adolescents is presented as an interactive network of “I” voices interpreted to reflect internal and external dialogue. In this way, self is understood within dialogical concepts of voices as multiple expressions. The study invited twelve gifted young adolescents to write freely about themselves over a six month period in an email journal project. Participants were recruited online and by word-of-mouth and they were able to negotiate their own levels of involvement. Access to the lives of individual young adolescents was sought in an out-of-school setting using narrative methods of personal writing in the form of journals sent as emails to the researcher. The role of the researcher was to act as a supportive listener who responded to participant-led emails and thereby facilitated the process of authoring that occurred across the data-gathering phase. The listening process involved responses that were affirming and designed to build trust. Data in the form of email texts were analysed using a close listening method that uncovered patterns of voices that were explicitly or subtly expressed by participants. The interpretation of voices highlighted the tensions and contradictions involved in the process of participants forming a “self” that emerged as multiple “I” voices. There were three key findings of the study. First, the gifted young adolescent participants each constructed a self around four key voices of Author, Achiever, Resistor/Co-operator and Self-Innovator. These voices were dialogical selfconstructions that showed multiplicity as a normal way of being. Second, the selfmaking processes of the gifted young adolescent participants were guided by a hierarchy of voices that were directed through self-awareness. Third, authoring in association with a responsive adult listener emerged as a dialogic space for promoting self-awareness and a language of self-expression among gifted young adolescents. The findings of the study contribute to knowledge about gifted young adolescents by presenting their own versions of “who” they are, perspectives that might differ from mainstream perceptions. Participants were shown to have highly diverse, complex and individual expressions that have implications for how well they are understood and supported by others. The use of email journals helped to create a synergy for self-disclosure and a safe space for self-expression where participants’ abilities to be themselves were encouraged. Increased self-awareness and selfknowledge among gifted young adolescents is vital to their self-formation and their management of self and others’ expectations. This study makes an original contribution to the field of self-study by highlighting the processes and complexities of young adolescents’ self-constructions. Through the innovative use of narrative methods and an inter-disciplinary approach, the voices of gifted young adolescents were privileged. At a practical level, the study can inform educators, policy-makers, parents and all those who seek to contribute to the well-being of gifted young adolescents.

The search for individualism : Self-expression through product personalisation

This research paper explores the impact product personalisation has upon product attachment and aims to develop a deeper understanding of why, how and if consumers choose to do so. The current research in this field is mainly based on attachment theories and is predominantly product specific. This paper researches the link between product attachment and personalisation through in-depth, semi-structured interviews, where the data has been thematically analysed and broken down into three themes, and nine sub-themes. It was found that participants did become more attached to products once they were personalised and the reasons why this occurred varied. The most common reasons that led to personalisation were functionality and usability, the expression of personality through a product and the complexity of personalisation. The reasons why participants felt connected to their products included strong emotions/memories, the amount of time and effort invested into the personalisation, a sense of achievement. Reasons behind the desire for personalisation included co-designing, expression of uniqueness/individualism and having choice for personalisation. Through theme and inter-theme relationships, many correlations were formed, which created the basis for design recommendations. These recommendations demonstrate how a designer could implement the emotions and reasoning for personalisation into the design process.

Attitudes, Ideologies and Self-Organisation : Information Load Minimisation in Multi-Agent Decision Making

Sophisticated models of human social behaviour are fast becoming highly desirable in an increasingly complex and interrelated world. Here, we propose that rather than taking established theories from the physical sciences and naively mapping them into the social world, the advanced concepts and theories of social psychology should be taken as a starting point, and used to develop a new modelling methodology. In order to illustrate how such an approach might be carried out, we attempt to model the low elaboration attitude changes of a society of agents in an evolving social context. We propose a geometric model of an agent in context, where individual agent attitudes are seen to self-organise to form ideologies, which then serve to guide further agent-based attitude changes. A computational implementation of the model is shown to exhibit a number of interesting phenomena, including a tendency for a measure of the entropy in the system to decrease, and a potential for externally guiding a population of agents towards a new desired ideology.

Quantum one-time programs

A one-time program is a hypothetical device by which a user may evaluate a circuit on exactly one input of his choice, before the device self-destructs. One-time programs cannot be achieved by software alone, as any software can be copied and re-run. However, it is known that every circuit can be compiled into a one-time program using a very basic hypothetical hardware device called a one-time memory. At first glance it may seem that quantum information, which cannot be copied, might also allow for one-time programs. But it is not hard to see that this intuition is false: one-time programs for classical or quantum circuits based solely on quantum information do not exist, even with computational assumptions. This observation raises the question, "what assumptions are required to achieve one-time programs for quantum circuits?" Our main result is that any quantum circuit can be compiled into a one-time program assuming only the same basic one-time memory devices used for classical circuits. Moreover, these quantum one-time programs achieve statistical universal composability (UC-security) against any malicious user. Our construction employs methods for computation on authenticated quantum data, and we present a new quantum authentication scheme called the trap scheme for this purpose. As a corollary, we establish UC-security of a recent protocol for delegated quantum computation.

Mussel-inspired bioceramics with self-assembled Ca-P/polydopamine composite nanolayer : preparation, formation mechanism, improved cellular bioactivity and osteogenic differentiation of bone marrow stromal cells

The nanostructured surface of biomaterials plays an important role in improving their in vitro cellular bioactivity as well as stimulating in vivo tissue regeneration. Inspired by the mussel’s adhesive versatility, which is thought to be due to the plaque–substrate interface being rich in 3,4-dihydroxy-L-phenylalamine (DOPA) and lysine amino acids, in this study we developed a self-assembly method to prepare a uniform calcium phosphate (Ca-P)/polydopamine composite nanolayer on the surface of b-tricalcium phosphate (b-TCP) bioceramics by soaking b-TCP bioceramics in Tris–dopamine solution. It was found that the addition of dopamine, reaction temperature and reaction time are three key factors inducing the formation of a uniform Ca-P/polydopamine composite nanolayer. The formation mechanism of a Ca-P/polydopamine composite nanolayer involved two important steps: (i) the addition of dopamine to Tris–HCl solution decreases the pH value and accelerates Ca and P ionic dissolution from the crystal boundaries of b-TCP ceramics; (ii) dopamine is polymerized to form self-assembled polydopamine film and, at the same time, nanosized Ca-P particles are mineralized with the assistance of polydopamine, in which the formation of polydopamine occurs simultaneously with Ca-P mineralization (formation of nanosized microparticles composed of calcium phosphate-based materials), and finally a self-assembled Ca-P/polydopamine composite nanolayer forms on the surface of the b-TCP ceramics. Furthermore, the formed self-assembled Ca-P/polydopamine composite nanolayer significantly enhances the surface roughness and hydrophilicity of b-TCP ceramics, and stimulates the attachment, proliferation, alkaline phosphate (ALP) activity and bone-related gene expression (ALP, OCN, COL1 and Runx2) of human bone marrow stromal cells. Our results suggest that the preparation of self-assembled Ca-P/polydopamine composite nanolayers is a viable method to modify the surface of biomaterials by significantly improving their surface physicochemical properties and cellular bioactivity for bone regeneration application.

Development, implementation and evaluation of a cancer survivor self-management care plan

Aim There is a growing population of people with cancer who experience physiological and psychological effects that persist long after treatment is complete. Interventions that enhance survivors’ self-management abilities might help offset these effects. The aim of this pilot study was to develop, implement and evaluate interventions tailored to assist patients to manage post-treatment health issues effectively. Method In this pre-post intervention cohort study, participants were recruited on completion of cancer treatment. Participants recruited preimplementation, who received usual care, comprised the control group. Participants recruited later formed the intervention group. In the intervention group, the Cancer Care Coordinator developed an individualised, structured Cancer Survivor Self-management Care Plan. Participants were interviewed on completion of treatment (baseline) and at three months. Assessments concerned health needs (CaSUN), self-efficacy in adjusting and coping with cancer and health-related quality of life (FACIT-B or FACT-C). The impact of the intervention was determined by independent t-tests of change scores. Results The intervention (n = 32) and control groups (n = 35) were comparable on demographic and clinical characteristics. Sample mean age was 54 + 10 years. Cancer diagnoses were breast (82%) and colorectal (18%). Statistically significant differences (p < 0.05) indicated improvement in the intervention group for: (a) functional well-being, from the FACIT, (Control: M = −0.69, SE = 0.91; Intervention: M = 3.04, SE = 1.13); and (b) self-efficacy in maintaining social relationships, (Control: M = −0.333, SE = 0.33; Intervention: M = 0.621, SE = 0.27). No significant differences were found in health needs, other subscales of quality of life, the extent and number of strategies used in coping and adjusting to cancer and in other domains of self-efficacy. Conclusions While the results should be interpreted with caution, due to the non-randomised nature of the study and the small sample size, they indicate the potential benefits of tailored self-management interventions warrant further investigation in this context.

Concerted HO2 elimination from alpha-Aminoalkylperoxyl free radicals : Experimental and theoretical evidence from the gas phase NH2 center dot CHCO2- + O-2 reaction

We have investigated the gas-phase reaction of the alpha-aminoacetate (glycyl) radical anion (NH2(sic)CHCO2-) with O-2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O-2 to form the hydroperoxyl radical (HO2(sic)) and an even-electron imine (NHCHCO2-), with experiments and master equation simulations revealing that reaction proceeds at the ion molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(sic) elimination mechanism in the NH2CH(OO(sic))CO2- peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus alpha-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (sic)NO to (sic)NO2 commonly encountered in peroxyl radical chemistry.

Fast, energy-efficient synthesis of luminescent carbon quantum dots

A simple, fast, energy and labour efficient, carbon dot synthesis method involving only the mixing of a saccharide and base is presented. Uniform, green luminescent carbon dots with an average size of 3.5 nm were obtained, without the need for additional energy input or external heating. Detection of formation moment for fructose-NaOH-produced carbon dots is also presented.

Self-organized vertically aligned single-crystal silicon nanostructures with controlled shape and aspect ratio by reactive plasma etching

The formation of vertically aligned single-crystalline silicon nanostructures via "self-organized" maskless etching in Ar+ H 2 plasmas is studied. The shape and aspect ratio can be effectively controlled by the reactive plasma composition. In the optimum parameter space, single-crystalline pyramid-like nanostructures are produced; otherwise, nanocones and nanodots are formed. This generic nanostructure formation approach does not involve any external material deposition. It is based on a concurrent sputtering, etching, hydrogen termination, and atom/radical redeposition and can be applied to other nanomaterials.

Single-step, rapid low-temperature synthesis of Si quantum dots embedded in an amorphous SiC matrix in high-density reactive plasmas

A simple, effective and innovative approach based on low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to rapidly synthesize Si quantum dots (QDs) embedded in an amorphous SiC (a-SiC) matrix at a low substrate temperature and without any commonly used hydrogen dilution. The experimental results clearly demonstrate that uniform crystalline Si QDs with a size of 3-4 nm embedded in the silicon-rich (carbon content up to 10.7at.%) a-SiC matrix can be formed from the reactive mixture of silane and methane gases, with high growth rates of ∼1.27-2.34 nm s-1 and at a low substrate temperature of 200 °C. The achievement of the high-rate growth of Si QDs embedded in the a-SiC without any commonly used hydrogen dilution is discussed based on the unique properties of the inductively coupled plasma-based process. This work is particularly important for the development of the all-Si tandem cell-based third generation photovoltaic solar cells.