Buckling in polymer monolayers: Molecular-weight dependence

We present systematic investigations of buckling in Langmuir monolayers of polyvinyl acetate formed at the air-water interface. On compression the polymer monolayers are converted to a continuous membrane with a thickness of ~2–3 nm of well-defined periodicity, lambdab. Above a certain surface concentration the membrane undergoes a morphological transition buckling, leading to the formation of striped patterns. The periodicity seems to depend on molecular weight as per the predictions of the gravity-bending buckling formalism of Milner et al. for fluidlike films on water. However anomalously low values of bending rigidity and Young's modulus are obtained using this formalism. Hence we have considered an alternative model of buckling-based solidlike films on viscoelastic substrates. The values of bending rigidity and Young's modulus obtained by this method, although lower than expected, are closer to the bulk values. Remarkably, no buckling is found to occur above a certain molecular weight. We have tried to explain the observed molecular-weight dependence in terms of the variation in isothermal compressive modulus of the monolayers with surface concentration as well as provided possible explanations for the obtained low values of mechanical properties similar to that observed for ultrathin polymer films.

Nicotine Dependence and Smoking Behaviour : A genetic and epidemiological study

The worldwide health burden caused by the tobacco epidemic highlights the importance of study-ing determinants of smoking behaviour and key factors sustaining nicotine dependence. Despite vast-ranging preventive efforts, smoking remains one of the most deleterious health behaviours, and its genetic and environmental factors warrant continuous investigation. The heritability of smoking behaviour and nicotine dependence has been suggested to be relatively high. Earlier smoking behaviour, nicotine dependence, socio-economic position and demographic factors have all been shown to be associated with smoking cessation. This thesis aimed to examine various aspects of smoking behaviour and nicotine dependence from an epidemiological and genetic per-spective. Data for Studies I and IV were obtained from the Older Finnish Twin Cohort, a postal health sur-vey conducted in 1975, 1981 and 1990 on same-sexed pairs and in 1996-1997 on male-female adult pairs. The number of ever-smoking participants was 8941 in Study I and 3069 in Study IV. Data for Studies II and III came from the Family Study of Cigarette Smoking - Vulnerability to Nicotine Addiction. This study is linked to the Older Finnish Twin Cohort with new data collec-tion during 2001-2006 that focused on smoking twin pairs and their family members. The meas-ures included intensive telephone interviews, blood samples and additional postal questionnaires. The numbers of ever-smoking participants was 1370 in Study II and 529 in Study III. Study I examined whether a genetic component underlies smoking behaviour among Finnish adults. Genetic factors were important in the amount smoked and smoking cessation, with about half of the phenotypic differences explained by genetic variance. A novel finding was that genetic influences on amount smoked and smoking cessation were largely independent of genetic influ-ences on age at initiation. This result has implications for defining phenotypes in the search for genes underlying smoking behaviour. Furthermore, even if smoking initiation is postponed to a later age, potential vulnerability to subsequent nicotine dependence cannot be completely inhib-ited. Study II investigated the effect of genetic and environmental factors on nicotine dependence, as measured by the novel multidimensional Nicotine Dependence Syndrome Scale (NDSS). This scale was validated in the Finnish data. The NDSS correlated highly with other established nico-tine dependence scales (FTND and DSM-IV), suggesting that this new scale would be a feasible and valid measure for identifying nicotine-dependent smokers among the ever-smoking popula-tion. About one-third of the phenotypic variation in nicotine dependence in this sample was ex-plained by genetic influences. Study III aimed at identifying chromosomal regions harbouring genes that influence smoking be-haviour and nicotine dependence. Linkage analysis of family data revealed that for smoker and nicotine dependence phenotypes as well as for co-morbidity between nicotine dependence and alcohol use signals on specific chromosome regions (chromosomes 2q33, 5q12, 5q34 7q21, 7q31, 10q25, 11p15, 20p13) exist. Results further support the hypothesis that smoking behaviour phe-notypes have a genetic background. Study IV examined associations of smoking behaviour, socio-economic position and transition of marital status with smoking cessation. Indicators of socio-economic position were important pre-dictors of smoking cessation even when adjusted for previous smoking behaviour. Getting married was associated with an increased probability of cessation in men, a finding confirmed among dis-cordant twin pairs. Thus, having a partner appears to have a positive impact on smoking cessation. In conclusion, nicotine dependence and smoking behaviour demonstrate significant genetic liabil-ity, but also substantial environmental influences among Finnish adults. Smoking initiation should be prevented or at least postponed to a later age. Although genetic factors are important in nicotine dependence and smoking behaviour, societal actions still have a primary role in tobacco control and smoking prevalence. Future studies should examine the complex interactions between genetic and environmental factors in nicotine dependence.

Subquadratic wavenumber dependence of the structural relaxation of supercooled liquid in the crossover regime

As a liquid is progressively supercooled toward its glass transition temperature, an intriguing weakening of the wavenumber (q) dependence of the structural relaxation time tau(q) in the intermediate-to-large q limit is observed both in experiments and simulation studies. Neither continuous Brownian diffusive dynamics nor discontinuous activated events can alone explain the anomalous wavenumber dependence. Here we use our recently developed theory that unifies the mode coupling theory for continuous dynamics, with the random first order transition theory treatment of activated discontinuous motion as a nucleationlike instanton process to understand the wavenumber dependence of density relaxation. The predicted smooth change in mechanism of relaxation from diffusive to activated, in the crossover regime, is wavevector dependent and appears to be responsible for the observed subquadratic,nalmost linear, q dependence of the relaxation time.

Isomerization dynamics in viscous liquids: Microscopic investigation of the coupling and decoupling of the rate to and from solvent viscosity and dependence on the intermolecular potential

A detailed investigation of viscosity dependence of the isomerization rate is carried out for continuous potentials by using a fully microscopic, self-consistent mode-coupling theory calculation of both the friction on the reactant and the viscosity of the medium. In this calculation we avoid approximating the short time response by the Enskog limit, which overestimates the friction at high frequencies. The isomerization rate is obtained by using the Grote-Hynes formula. The viscosity dependence of the rate has been investigated for a large number of thermodynamic state points. Since the activated barrier crossing dynamics probes the high-frequency frictional response of the liquid, the barrier crossing rate is found to be sensitive to the nature of the reactant-solvent interaction potential. When the solute-solvent interaction is modeled by a 6-12 Lennard-Jones potential, we find that over a large variation of viscosity (eta), the rate (k) can indeed be fitted very well to a fractional viscosity dependence: (k similar to eta(-alpha)), with the exponent alpha in the range 1 greater than or equal to alpha >0. The calculated values of the exponent appear to be in very good agreement with many experimental results. In particular, the theory, for the first time, explains the experimentally observed high value of alpha even at the barrier frequency, omega(b). similar or equal to 9 X 10(12) s(-1) for the isomerization reaction of 2-(2'-propenyl)anthracene in liquid eta-alkanes. The present study can also explain the reason for the very low value of vb observed in another study for the isomerization reaction of trans-stilbene in liquid n-alkanes. For omega(b) greater than or equal to 2.0 X 10(13) s(-1), we obtain alpha similar or equal to 0, which implies that the barrier crossing rate becomes identical to the transition-state theory predictions. A careful analysis of isomerization reaction dynamics involving large amplitude motion suggests that the barrier crossing dynamics itself may become irrelevant in highly viscous liquids and the rate might again be coupled directly to the viscosity. This crossover is predicted to be strongly temperature dependent and could be studied by changing the solvent viscosity by the application of pressure. (C) 1999 American Institute of Physics. [S0021-9606(9950514-X].

Strain Rate Dependence of Plastic Flow in Ce-based Bulk Metallic Glass During Nanoindentation

The strain rate dependence of plastic deformation of Ce60Al15CU10Ni15 bulk metallic glass was studied by nanoindentation. Even though the ratio of room temperature to the glass transition temperature was very high (0.72) for this alloy, the plastic deformation was dominated by shear banding under nanoindentation. The alloy exhibited a critical loading rate dependent serrated flow feature. That is, with increasing loading rate, the alloy exhibited a transition from less prominent serrated flow to pronounced serrated flow during continuous loading but from serrated to smoother flow during stepped loading.

Wavelength dependence of light-induced domain nucleation in MgO-doped congruent LiNbO3 crystal

Within the wavelength range from 351 to 799 nm, the different reductions of nucleation field induced by the focused continuous laser irradiation are achieved in the 5 mol % MgO-doped congruent LiNbO3 crystals. The reduction proportion increases exponentially with decreasing irradiation wavelength and decreases exponentially with increasing irradiation wavelength. At one given wavelength, the reduction proportion increases exponentially with increasing irradiation intensity. An assumption is proposed that the reduction of nucleation field is directly related to the defect structure of crystal lattice generated by the complex coaction of incident irradiation field and external electric field. (c) 2007 American Institute of Physics.

Compact continuous-wave blue lasers by direct frequency doubling of laser diodes with periodically poled lithium niobate waveguide crystals

A compact continuous-wave blue laser has been demonstrated by direct frequency doubling of a laser diode with a periodically poled lithium niobate (PPLN) waveguide crystal. The optimum PPLN temperature is near 28 degreesC, and the dependence of waveguide crystals on crystal temperature is less sensitive than that of bulk crystals. A total of 14.8 mW of 488-nm laser power has been achieved. (C) 2005 Optical Society of America.

Thickness dependence of structure and optical properties of silver films deposited by magnetron sputtering

A series of silver films with different thickness were prepared under identical conditions by direct current magnetron sputtering. The optical properties of the silver films were measured using spectrophotometric techniques and the optical constants were calculated from reflection and transmission measurements made at near normal incidence. The results show that the optical properties and constants are affected by films' thickness. Below the critical thickness of 17 nm at which Ag film forms a continuous film, the optical properties and constants vary significantly as the thickness of films increases and then tends to a stable value which is reached at 41 nm. X-ray diffraction measurements were carried out to examine the structure and stress evolution of the Ag films as a function of films' thickness. It was found that the interplanar distance of (111) orientation decreases when the film thickness increases and tends to be close to that of bulk material. The compressive strains also decrease with increasing thickness. (C) 2007 Published by Elsevier B.V.

Quasi-continuous-wave operation of AlGaAs/GaAs quantum cascade lasers

Quasi-continuous-wave operation of AlGaAs/GaAs-based quantum cascade lasers (lambda similar to 9 mu m) up to 165 K is reported. The strong temperature dependence of the threshold current density and its higher value in high duty cycle is investigated in detail. The self-heating effect in the active region is explored by changing the operating duty cycles. The degradation of lasing performance with temperature is explained. (c) 2005 Elsevier B.V. All rights reserved.

Linear energy transfer dependence of the effects of carbon ion beams on adventitious shoot regeneration from in vitro leaf explants of Saintpaulia ionahta

Purpose: To determine the effects of carbon ion beams with five different linear energy transfer (LET) values on adventitious shoots from in vitro leaf explants of Saintpaulia ionahta Mauve cultivar with regard to tissue increase, shoots differentiation and morphology changes in the shoots. Materials and methods: In vitro leaf explant samples were irradiated with carbon ion beams with LET values in the range of 31 similar to 151 keV/mu m or 8 MeV of X-rays (LET 0.2 keV/mu m) at different doses. Fresh weight increase, surviving fraction and percentage of the explants with regenerated malformed shoots in all the irradiated leaf explants were statistically analysed. Results: The fresh weight increase (FWI) and surviving fraction (SF) decreased dramatically with increasing LET at the same doses. In addition, malformed shoots, including curliness, carnification, nicks and chlorophyll deficiency, occurred in both carbon ion beam and X-ray irradiations. The induction frequency with the former, however, was far more than that with the X-rays. Conclusions: This work demonstrated the LET dependence of the relative biological effectiveness (RBE) of tissue culture of Saintpaulia ionahta according to 50% FWI and 50% SF. After irradiating leaf explants with 5 Gy of a 221 MeV carbon ion beam having a LET value of 96 keV/mu m throughout the sample, a chlorophyll-deficient (CD) mutant, which could transmit the character of chlorophyll deficiency to its progeny through three continuous tissue culture cycles, and plantlets with other malformations were obtained.

Effect of chain-length dependence of interaction parameter on spinodals for polydisperse polymer blends

The chain-length dependence of the Flory-Huggins (FH) interaction parameter is introduced into the FH lattice theory for polydisperse polymer-blend systems. The spinodals are calculated for the model polymer blends with different chain lengths and distributions. It is found that all the related variables r(n), r(w), r(z), and chain-length distribution, have effects on the spinodals for polydisperse polymer blends.

Green function for the diffusion limit of one-dimensional continuous time random walks

It is shown how the fractional probability density diffusion equation for the diffusion limit of one-dimensional continuous time random walks may be derived from a generalized Markovian Chapman-Kolmogorov equation. The non-Markovian behaviour is incorporated into the Markovian Chapman-Kolmogorov equation by postulating a Levy like distribution of waiting times as a kernel. The Chapman-Kolmogorov equation so generalised then takes on the form of a convolution integral. The dependence on the initial conditions typical of a non-Markovian process is treated by adding a time dependent term involving the survival probability to the convolution integral. In the diffusion limit these two assumptions about the past history of the process are sufficient to reproduce anomalous diffusion and relaxation behaviour of the Cole-Cole type. The Green function in the diffusion limit is calculated using the fact that the characteristic function is the Mittag-Leffler function. Fourier inversion of the characteristic function yields the Green function in terms of a Wright function. The moments of the distribution function are evaluated from the Mittag-Leffler function using the properties of characteristic functions and a relation between the powers of the second moment and higher order even moments is derived. (C) 2004 Elsevier B.V. All rights reserved.

Discrete and continuous compositions

This paper examines a dataset which is modeled well by the Poisson-Log Normal process and by this process mixed with Log Normal data, which are both turned into compositions. This generates compositional data that has zeros without any need for conditional models or assuming that there is missing or censored data that needs adjustment. It also enables us to model dependence on covariates and within the composition

Pan-Arctic and regional sea ice predictability: initialization month dependence

Seasonal-to-interannual predictions of Arctic sea ice may be important for Arctic communities and industries alike. Previous studies have suggested that Arctic sea ice is potentially predictable but that the skill of predictions of the September extent minimum, initialized in early summer, may be low. The authors demonstrate that a melt season “predictability barrier” and two predictability reemergence mechanisms, suggested by a previous study, are robust features of five global climate models. Analysis of idealized predictions with one of these models [Hadley Centre Global Environment Model, version 1.2 (HadGEM1.2)], initialized in January, May and July, demonstrates that this predictability barrier exists in initialized forecasts as well. As a result, the skill of sea ice extent and volume forecasts are strongly start date dependent and those that are initialized in May lose skill much faster than those initialized in January or July. Thus, in an operational setting, initializing predictions of extent and volume in July has strong advantages for the prediction of the September minimum when compared to predictions initialized in May. Furthermore, a regional analysis of sea ice predictability indicates that extent is predictable for longer in the seasonal ice zones of the North Atlantic and North Pacific than in the regions dominated by perennial ice in the central Arctic and marginal seas. In a number of the Eurasian shelf seas, which are important for Arctic shipping, only the forecasts initialized in July have continuous skill during the first summer. In contrast, predictability of ice volume persists for over 2 yr in the central Arctic but less in other regions.

On Approximate KKT Condition and its Extension to Continuous Variational Inequalities

In this work, we introduce a necessary sequential Approximate-Karush-Kuhn-Tucker (AKKT) condition for a point to be a solution of a continuous variational inequality, and we prove its relation with the Approximate Gradient Projection condition (AGP) of Garciga-Otero and Svaiter. We also prove that a slight variation of the AKKT condition is sufficient for a convex problem, either for variational inequalities or optimization. Sequential necessary conditions are more suitable to iterative methods than usual punctual conditions relying on constraint qualifications. The AKKT property holds at a solution independently of the fulfillment of a constraint qualification, but when a weak one holds, we can guarantee the validity of the KKT conditions.