Generalized self-assembly of scalable two-dimensional transition metal oxide nanosheets

Two-dimensional (2D) transition metal oxide systems present exotic electronic properties and high specific surface areas, and also demonstrate promising applications ranging from electronics to energy storage. Yet, in contrast to other types of nanostructures, the question as to whether we could assemble 2D nanomaterials with an atomic thickness from molecules in a general way, which may give them some interesting properties such as those of graphene, still remains unresolved. Herein, we report a generalized and fundamental approach to molecular self-assembly synthesis of ultrathin 2D nanosheets of transition metal oxides by rationally employing lamellar reverse micelles. It is worth emphasizing that the synthesized crystallized ultrathin transition metal oxide nanosheets possess confined thickness, high specific surface area and chemically reactive facets, so that they could have promising applications in nanostructured electronics, photonics, sensors, and energy conversion and storage devices.

The mesenchymal-to-epithelial reverting transition is enriched in metastatic castration resistant prostate cancer and correlates with poor survival

Despite recent recognition that the epithelial-mesenchymal transition (EMT) program acts in a dynamic manner (termed Epithelial to Mesenchymal Plasticity or EMP) during carcinoma metastasis, it has largely been ignored in the discovery and development of EMT-targeted therapies. In part, this has stemmed from a lack of preclinical models that can mimic the full dynamic nature of EMP and the perception that the EMT-reverting transition [or mesenchymal-epithelial reverting transition; (MErT)] is a mere antithesis of EMT. The objective of this study was to develop the first PCa model capable of recapitulating the dynamic nature of EMP.

Crystal structure of 3-acetylcoumarin-o-aminobenzoylhydrazone and synthesis, spectral and thermal studies of its transition metal complexes

Transition metal [Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)] complexes of a new Schiff base, 3-acetylcoumarin-o-aminobenzoylhydrazone were synthesized and characterized by elemental analyses, magnetic moments, conductivity measurements, spectral [Electronic, IR, H-1 and C-13 NMR, EPR] and thermal studies. The ligand crystallizes in the monoclinic system, space group P2(1)/n with a = 9.201(5), b = 16.596( 9), c = 11.517(6) angstrom, beta= 101.388(9)degrees, V = 1724.2 (17) angstrom(3) and Z = 4. Conductivity measurements indicated Mn(II) and Co(II) complexes to be 1 : 1 electrolytes whereas Ni(II), Cu(II), Zn(II) and Cd(II) complexes are non-electrolytes. Electronic spectra reveal that all the complexes possess four-coordinate geometry around the metal.

The glass transition and crystallization kinetic studies on BaNaB9O15 glasses

Transparent glasses of BaNaB9O15 (BNBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were, respectively, confirmed by x-ray powder diffraction and differential scanning calorimetry (DSC). The glass transition and crystallization parameters were evaluated under non-isothermal conditions using DSC. The correlation between the heating rate dependent glass transition and the crystallization temperatures was studied and the Kauzmann temperature was deduced for BNBO glass plates and powdered samples. The values of the Kauzmann temperature for the plates and powdered samples were 776 K and 768 K, respectively. An approximation- free method was used to evaluate the crystallization kinetic parameters for the BNBO glass samples. The effect of the sample thickness on the crystallization kinetics of BNBO glasses was also investigated.

Effect of Polymer Grafting on the Bilayer Gel to Liquid-Crystalline Transition

Grafted polymers oil the surface of lipid membranes have potential applications in liposome-based drug delivery and Supported membrane systems. The effect of polymer grafting on the phase behavior of bilayers made up of single-tail lipids is investigated using dissipative particle dynamics. The bilayer is maintained in a tensionless state using a barostat. Simulations are carried Out by varying the grafting fraction, G(f), defined as the ratio of the number of polymer molecules to the number of lipid molecules, and the length of the lipid tails. At low G(f), the bilayer shows I sharp transition from the gel (L-beta) to the liquid-crystalline (L-alpha) phase. This main melting transition temperature is lowered as G(f) is increased, and above a critical value of G(f), the interdigitated L-beta I phase is observed prior to the main transition. The temperature range over which the intermediate phases are observed is a function of the lipid tail length and G(f). At higher grafting fractions, the presence of the L-beta I, phase is attributed to the increase in the area per head group due to the lateral pressure exerted by the polymer brush. The areal expansion and decrease in the melting temperatures as a function of G(f) were found to follow the scalings predicted by the self-consistent mean field theories for grafted polymer membranes. Our study shows that the grafted polymer density can be used to effectively control the temperature range and occurrence of a given bilayer phase.

Transition to parenthood after assisted reproductive treatment: Follow-up study of singleton pregnancies

Infertility treatments are relatively easily available in most Western countries today, but the psychological consequences of these high-tech treatments have scarcely been addressed. The purpose of this controlled longitudinal study was to explore the early environment of the infant born by assisted reproductive treatment (ART). We focused on the parents mental well-being, marital relations and experience of parenting. In addition to this, we assessed parent child interaction and parents mental representations of their child after long-standing infertility and several unsuccessful ART attempts. The subjects were infertile couples who achieved a singleton pregnancy by in vitro fertilization (IVF) or intracytoplasmic sperm injection (ICSI). The control group comprised of spontaneously conceiving couples with singleton pregnancies. ART women showed fewer depressive symptoms than controls during pregnancy and after delivery, but the difference vanished by the end of the child s first year. ART men consistently had lower levels of anxiety symptoms, sleeping difficulties, and social dysfunction than control men. Control women experienced a decrease in dyadic consensus during the child s first year, which did not happen among ART women. After the child was born, ART men reported a higher level of sexual affection compared with control men. Psychic symptoms and stressful life events were differently related to marital relations in ART and control groups. The parenting experiences of ART mothers were in general at a higher level, compared with controls, and they changed in a positive direction during the child s first year. Fathering experiences were at the same level in both groups, and they changed positively in both groups by the end of the child s first year. The parenting experiences of ART mothers and fathers were more resilient to certain child-related stressors than those of control group. Both mothers and fathers with long-term infertility showed more sensitive behaviour with their child in toddler-age than in infancy. Correspondingly, children s cooperation increased. Mothers often mentioned a fear of miscarriage and difficulty in creating representations of the child during pregnancy. Descriptions of the infants were mainly rich, vivid and loaded with positive features. In conclusion, ART parents in general seem to adapt well to the transition to parenthood. Former infertility and ART do not seem to constitute a risk for parents mental health, marital relations or experience of parenting. Even longstanding infertility with several unsuccessful treatment attempts did not create a risk as regards parenting behaviour or parents mental representations of their child. In this group, however, women were found to have fear for losing the child and difficulty in creating representations of the child during pregnancy, which in some cases may indicate need for psychosocial support. Even though our results are encouraging, infertility and infertility treatments are generally considered as a stressful experience. It is a challenge for health authorities to recognize those couples who need professional help to overcome the distressing experiences of infertility and ART.

Straw Performance Studies and Quality Assurance for the ATLAS Transition Radiation Tracker

The Transition Radiation Tracker (TRT) of the ATLAS experiment at the LHC is part of the Inner Detector. It is designed as a robust and powerful gaseous detector that provides tracking through individual drift-tubes (straws) as well as particle identification via transition radiation (TR) detection. The straw tubes are operated with Xe-CO2-O2 70/27/3, a gas that combines the advantages of efficient TR absorption, a short electron drift time and minimum ageing effects. The modules of the barrel part of the TRT were built in the United States while the end-cap wheels are assembled at two Russian institutes. Acceptance tests of barrel modules and end-cap wheels are performed at CERN before assembly and integration with the Semiconductor Tracker (SCT) and the Pixel Detector. This thesis first describes simulations the TRT straw tube. The argon-based acceptance gas mixture as well as two xenon-based operating gases are examined for its properties. Drift velocities and Townsend coefficients are computed with the help of the program Magboltz and used to study electron drift and multiplication in the straw using the software Garfield. The inclusion of Penning transfers in the avalanche process leads to remarkable agreements with experimental data. A high level of cleanliness in the TRT s acceptance test gas system is indispensable. To monitor gas purity, a small straw tube detector has been constructed and extensively used to study the ageing behaviour of the straw tube in Ar-CO2. A variety of ageing tests are presented and discussed. Acceptance tests for the TRT survey dimensions, wire tension, gas-tightness, high-voltage stability and gas gain uniformity along each individual straw. The thesis gives details on acceptance criteria and measurement methods in the case of the end-cap wheels. Special focus is put on wire tension and straw straightness. The effect of geometrically deformed straws on gas gain and energy resolution is examined in an experimental setup and compared to simulation studies. An overview of the most important results from the end-cap wheels tested up to this point is presented.

Melting of an Anchored Bilayer: Molecular Dynamics Simulations of the Structural Transition in (CnH2n+1NH3)(2)PbI4 (n=12, 14, 16, 18)

The thermally driven Structural phase transition in the organic-inorganic hybrid perovskite (CnH2n+1NH3)(2)PbI4 has been investigated using molecular dynamics (MD) simulations. This system consists of positively charged alkyl-amine chains anchored to a rigid negatively charged PbI4 sheet with the chains organized as bilayers with a herringbone arrangement. Atomistic simulations were performed using ail isothermal-isobaric ensemble over a wide temperature range from 65 to 665 K for different alkyl chain lengths, n = 12, 14, 16, and 18. The simulations are able to reproduce the essential Features of the experimental observations of this system, including the existence of a transition, the linear variation of the transition temperature with alkyl chain length, and the expansion of the bilayer thickness at the transition. By use of the distance fluctuation Criteria, it is Shown that the transition is associated With a Melting of the alkyl chains of the anchored bilayer. Ail analysis of the conformation of the alkyl chains shows increased disorder in the form of gauche defects above due melting transition. Simulations also show that the melting transition is characterized by the complete disappearance of all-trans alkyl chains in the anchored bilayer, in agreement with experimental observations. A conformationally disordered chain has a larger effective cross-sectional area, and above due transition a uniformly tilted arrangement of the anchored chains call no longer be Sustained. At the melt the angular distribution of the orientation of the chains are 110 longer uniform; the chains are splayed allowing for increased space for individual chains of the anchored bilayer. This is reflected in a sharp rise in the ratio of the mean head-to-head to tail-to-tail distance of the chains of the bilayer at the transition resulting in in expansion of the bilayer thickness. The present MD simulations provide a simple explanation as to how changes in conformation of individual alkyl-chains gives rise to the observed increase in the interlayer lattice spacing of (CnH2n+1NH3)(2)PbI4 at the melting transition.

Evolution of isolated streamwise vortices in the late stages of boundary layer transition

Experiments were conducted with two, smooth hills, lying well within the boundary layer over a flat plate mounted in a wind tunnel. One hill was shallow, with peak height 1.5 mm and width 50 mm; the other, steep, 3 mm high and 30 mm wide. Since the hills occupied one-half of the tunnel span, streamwise vorticity formed near the hills' edge. At a freestream speed of 3.5 m/s, streaks formed with inflectional wall-normal and spanwise velocity profiles but without effecting transition. Transition, observed at 7.5 m/s, took different routes with the two hills. With the steep hill, streamwise velocity signals exhibited the passage of a wave packet which intensified before breakdown to turbulence. With the shallow hill there was a broad range of frequencies present immediately downstream of the hill. These fluctuations grew continuously and transition occurred within a shorter distance. Since the size of the streamwise vorticity generated at the hill edge is of the order of the hill height, the shallow hill generates vorticity closer to the wall and supports an earlier transition, whereas the steep hill creates a thicker vortex and associated streaks which exhibit oscillations due to their own instability as an additional precursor stage before transition.

Communication and Political Crisis: Media, Politics and Governance in a Globalized Public Sphere

Communication and Political Crisis explores the role of the global media in a period of intensifying geopolitical conflict. Through case studies drawn from domestic and international political crises such as the conflicts in the Middle East and Ukraine, leading media scholar Brian McNair argues that the digitized, globalized public sphere now confronted by all political actors has produced new opportunities for social progress and democratic reform, as well as new channels for state propaganda and terrorist spectaculars such as those performed by the Islamic State and Al Qaeda. In this major work, McNair argues that the role of digital communication will be crucial in determining the outcome of pressing global issues such as the future of feminism and gay rights, freedom of speech and media, and democracy itself.

Tuning the beta-turn segment in designed peptide beta-hairpins: Construction of a stable type I ' beta-turn nucleus and hairpin-helix transition promoting segments

Designed octapeptides Boc-Leu-Val-Val-Aib-(D)Xxx-Leu- Val-Val-OMe ((D)Xxx = (D)Ala, 3a; (D)Val, 3c and (D)Pro, 5a) and Boc-Leu-Phe-Val-Aib-DAla-Leu-Phe-Val-OMe (3b) have been investigated to construct models of a stable type I' beta-turn nucleated hairpin and to generate systems for investigating helix-hairpin conformational transitions. Peptide 5a, which contains a central Aib-(D)Pro segment, is shown to adopt a stable type I' beta-turn nucleated hairpin structure, stabilized by four cross-strand hydrogen bonds. The stability of the structure in diverse solvents is established by the observation of all diagnostic NOEs expected in a beta-hairpin conformation. Replacement of (D)Pro5 by (D)Ala/(D)Val (3a-c) results in sequences that form beta-hairpins in hydrogen bonding solvents like CD3OH and DMSO-d(6). However, in CDCl3 evidence for population of helical conformations is obtained. Peptide 6b (Boc-Leu-Phe-Val-Aib-Aib-Leu-Phe-Val-OMe), which contains a centrally positioned Aib-Aib segment, provides a clear example of a system, which exhibits a helical conformation in CDCl3 and a significant population of both helices and hairpins in CD3OH and DMSO-d(6). The coexistence of multiple conformations is established by the simultaneous observation of diagnostic NOEs. Control over stereochemistry of the central beta-turn permits generation of models for robust beta-hairpins and also for the construction of systems that may be used to probe helix-hairpin conformational transitions. (c) 2006 Wiley Periodicals, Inc.

Dimensional Reduction Near the Deconfinement Transition

When ordinary nuclear matter is heated to a high temperature of ~ 10^12 K, it undergoes a deconfinement transition to a new phase, strongly interacting quark-gluon plasma. While the color charged fundamental constituents of the nuclei, the quarks and gluons, are at low temperatures permanently confined inside color neutral hadrons, in the plasma the color degrees of freedom become dominant over nuclear, rather than merely nucleonic, volumes. Quantum Chromodynamics (QCD) is the accepted theory of the strong interactions, and confines quarks and gluons inside hadrons. The theory was formulated in early seventies, but deriving first principles predictions from it still remains a challenge, and novel methods of studying it are needed. One such method is dimensional reduction, in which the high temperature dynamics of static observables of the full four-dimensional theory are described using a simpler three-dimensional effective theory, having only the static modes of the various fields as its degrees of freedom. A perturbatively constructed effective theory is known to provide a good description of the plasma at high temperatures, where asymptotic freedom makes the gauge coupling small. In addition to this, numerical lattice simulations have, however, shown that the perturbatively constructed theory gives a surprisingly good description of the plasma all the way down to temperatures a few times the transition temperature. Near the critical temperature, the effective theory, however, ceases to give a valid description of the physics, since it fails to respect the approximate center symmetry of the full theory. The symmetry plays a key role in the dynamics near the phase transition, and thus one expects that the regime of validity of the dimensionally reduced theories can be significantly extended towards the deconfinement transition by incorporating the center symmetry in them. In the introductory part of the thesis, the status of dimensionally reduced effective theories of high temperature QCD is reviewed, placing emphasis on the phase structure of the theories. In the first research paper included in the thesis, the non-perturbative input required in computing the g^6 term in the weak coupling expansion of the pressure of QCD is computed in the effective theory framework at an arbitrary number of colors. The two last papers on the other hand focus on the construction of the center-symmetric effective theories, and subsequently the first non-perturbative studies of these theories are presented. Non-perturbative lattice simulations of a center-symmetric effective theory for SU(2) Yang-Mills theory show --- in sharp contrast to the perturbative setup --- that the effective theory accommodates a phase transition in the correct universality class of the full theory. This transition is seen to take place at a value of the effective theory coupling constant that is consistent with the full theory coupling at the critical temperature.

Dynamo onset as a first-order transition: Lessons from a shell model for magnetohydrodynamics

We carry out systematic and high-resolution studies of dynamo action in a shell model for magnetohydro-dynamic (MHD) turbulence over wide ranges of the magnetic Prandtl number Pr-M and the magnetic Reynolds number Re-M. Our study suggests that it is natural to think of dynamo onset as a nonequilibrium first-order phase transition between two different turbulent, but statistically steady, states. The ratio of the magnetic and kinetic energies is a convenient order parameter for this transition. By using this order parameter, we obtain the stability diagram (or nonequilibrium phase diagram) for dynamo formation in our MHD shell model in the (Pr-M(-1), Re-M) plane. The dynamo boundary, which separates dynamo and no-dynamo regions, appears to have a fractal character. We obtain a hysteretic behavior of the order parameter across this boundary and suggestions of nucleation-type phenomena.

Monoclinic polymorph of Boc-Trp-Ile-Ala-Aib-Ile-Val-Aib-Leu-Aib-Pro-OMe(anhydrous). Parallel packing of 3(10)-/alpha-helices and a transition of helix type

The structures of two crystal forms of Boc-Trp-Ile-Ala-Aib-Ile-Val-Aib-Leu-Aib-Pro-OMe have been determined. The triclinic form (P1, Z = 1) from DMSO/H2O crystallizes as a dihydrate (Karle, Sukumar & Balaram (1986) Proc, Natl, Acad. Sci. USA 83, 9284-9288). The monoclinic form (P2(1), Z = 2) crystallized from dioxane is anhydrous. The conformation of the peptide is essentially the same in both crystal system, but small changes in conformational angles are associated with a shift of the helix from a predominantly alpha-type to a predominantly 3(10)-type. The r.m.s. deviation of 33 atoms in the backbone and C beta positions of residues 2-8 is only 0.29 A between molecules in the two polymorphs. In both space groups, the helical molecules pack in a parallel fashion, rather than antiparallel. The only intermolecular hydrogen bonding is head-to-tail between helices. There are no lateral hydrogen bonds. In the P2(1) cell, a = 9.422(2) A, b = 36.392(11) A, c = 10.548(2) A, beta = 111.31(2) degrees and V = 3369.3 A for 2 molecules of C60H97N11O13 per cell.

Retirement Transition and Well-being : A 16-year Longitudinal Study

The ageing of the labour force and falling employment rates have forced policy makers in industrialized countries to find means of increasing the well-being of older workers and of lengthening their work careers. The main objective of this thesis was to study longitudinally how health, functional capacity, subjective well-being, and lifestyle change as people grow older, and what effect retirement has on these factors and on their relationships. The present study is a follow-up questionnaire study of Finnish municipal workers, conducted in 1981 to 1997 at the Finnish Institute of Occupational Health. In 1981, a postal questionnaire was sent to 7344 municipal workers in different parts of Finland. The respondents were born between 1923 and 1937. A total of 6257 persons responded to the first questionnaire. In the end, a total of 3817 persons had responded to all four (1981, 1985, 1992, 1997) questionnaires. (The response rate was 69% of the living participants). Cross-tabulations, comparison of means, logistic regression analyses and general linear models with repeated measures were used to derive the results. The transition from work life to retirement, and the following years as a pensioner were associated with many changes. Involvement in various activities increased during the transition stage but later decreased to the previous level. Physical exercise was an exception: it became increasingly popular over the years. Perceived health improved markedly from the working stage to the retirement transition stage, even though morbidity increased steadily during the follow-up. On the other hand, functional capacity decreased over the follow-up, especially among those who were occupationally active until the retirement stage. Subjective well-being remained stable during the follow-up period. There were, however, great differences based on the type of work, favouring those whose work had been mental in nature. The impact of activity level on maintaining well-being became greater during the follow-up, whereas the effect of physical functioning diminished. Good physical functioning and an active life-style contributed to staying on at work until normal retirement age. Also work-related factors, i.e. possibilities for development and influence at work, responsibility for others, meaningful work, and satisfaction with working time arrangements were positively related to continuing working. The transition from work to retirement had a positive impact on a person s health and functional capacity. The study results support the view that it should be possible to ease one s work pace during the last years of a work career. This might lower the threshold between work and retirement and convince people that there will still be time to enjoy retirement also a few years later.