Evidence of clustering in an aqueous electrolyte solution: a small-angle X-ray scattering study

The work reported hen was motivated by a desire to verify the existence of structure - specifically MP-rich clusters induced by sodium bromide (NaBr) in the ternary liquid mixture 3-methylpyridine (Mf) + water(W) + NaBr. We present small-angle X-ray scattering (SAXS) measurements in this mixture. These measurements were obtained at room temperature (similar to 298 K) in the one-phase region (below the relevant lower consolute points, T(L)s) at different values of X (i.e., X = 0.02 - 0.17), where X is the weight fraction of NaBr in the mixture. Cluster-size distribution, estimated on the assumption that the clusters are spherical, shows systematic behaviour in that the peak of the distribution shifts rewards larger values of cluster radius as X increases. The largest spatial extent of the clusters (similar to 4.5 nm) is seen at X = 0.17. Data analysis assuming arbitrary shapes and sizes of clusters gives a limiting value of cluster size (- 4.5 nm) that is not very sensitive to X. It is suggested that the cluster size determined may not be the same as the usual critical-point fluctuations far removed from the critical point (T-L). The influence of the additional length scale due to clustering is discussed from the standpoint of crossover from Ising to mean-field critical behaviour, when moving away from the T-L.

Hardness of a surface containing uniformly spaced pyramidal asperities

Pyramidal asperities of different apical angle were machined on a flat copper surface. Hardness was estimated from the load-displacement graphs obtained by pressing a spherical rigid indenter onto the asperities. The variation of hardness with apical angle and pitch was recorded with a view to contributing to the development of a general framework for relating measured hardness to the surface roughness.

X-ray diffraction of permalloy nanoparticles fabricated by laser ablation in water

Permalloy (NiFeMo) nanoparticles were fabricated by laser ablation of bulk material in water with a UV pulsed laser. Transmission electron microscope images showed that approximately spherical particles about 50 nm in diameter were formed in the ablation process. All diffraction peaks corresponding to the bulk material were present in the nanoparticles. In addition to these peaks several new peaks were observed in the nanoparticles, which were attributed to nickel oxide.

Remarkable Capacity Retention of Nanostructured Manganese Oxide upon Cycling as an Electrode Material for Supercapacitor

Electrochemical capacity retention of nearly X-ray amorphous nanostructured manganese oxide (nanoMnO2) synthesized by mixing directly KMnO4 with ethylene glycol under ambient conditions for supercapacitor studies is enhanced significantly. Although X-ray diffraction (XRD) pattern of nanoMnO2 shows poor crystallinity, it is found that by Mn K-edge X-ray absorption near edge structure (XANES) measurement that the nanoMnO2 obtained is locally arranged in a δ-MnO2-type layered structure composed of edge-shared network of MnO6 octahedra. Field emission scanning electron microscopy and XANES measurements show that nanoMnO2 contains nearly spherical shaped morphology with δ-MnO2 structure, and 1D nanorods of α-MnO2 type structure (powder XRD) in the annealed (600 °C) sample. Volumetric nitrogen adsorption−desorption isotherms, inductively coupled plasma analysis, and thermal analysis are carried out to obtain physicochemical properties such as surface area (230 m2 g−1), porosity of nanoMnO2 (secondary mesopores of diameter 14.5 nm), water content, composition, etc., which lead to the promising electrochemical properties as an electrode for supercapacitor. The nanoMnO2 shows a very high stability even after 1200 cycles with capacity retention of about 250 F g−1.

Computation of Diffuse Solar Radiation

A technique for computing the spectral and angular (both the zenith and azimuthal) distribution of the solar energy reaching the surface of earth and any other plane in the atmosphere has been developed. Here the computer code LOWTRAN is used for getting the atmospheric transmittances in conjunction with two approximate procedures: one based on the Eddington method and the other on van de Hulst's adding method, for solving the equation of radiative transfer to obtain the diffuse radiation in the cloud-free situation. The aerosol scattering phase functions are approximated by the Hyeney-Greenstein functions. When the equation of radiative transfer is solved using the adding method, the azimuthal and zenith angle dependence of the scattered radiation is evaluated, whereas when the Eddington technique is utilized only the total downward flux of scattered solar radiation is obtained. Results of the diffuse and beam components of solar radiation received on surface of earth compare very well with those computed by other methods such as the more exact calculations using spherical harmonics and when atmospheric conditions corresponding to that prevailing locally in a tropical location (as in India) are used as inputs the computed values agree closely with the measured values.

Scheme of squares: Part I. Systems formalism for potentiostatic studies

The so-called “Scheme of Squares”, displaying an interconnectivity of heterogeneous electron transfer and homogeneous (e.g., proton transfer) reactions, is analysed. Explicit expressions for the various partial currents under potentiostatic conditions are given. The formalism is applicable to several electrode geometries and models (e.g., semi-infinite linear diffusion, rotating disk electrodes, spherical or cylindrical systems) and the analysis is exact. The steady-state (t→∞) expressions for the current are directly given in terms of constant matrices whereas the transients are obtained as Laplace transforms that need to be inverted by approximation of numerical methods. The methodology employs a systems approach which replaces a system of partial differential equations (governing the concentrations of the several electroactive species) by an equivalent set of difference equations obeyed by the various partial currents.

Copper-doped mesoporous silica nanospheres, a promising immunomodulatory agent for inducing osteogenesis

The application of mesoporous silica nanospheres (MSNs) loaded with drugs/growth factors to induce osteogenic differentiation of stem cells has been trialed by a number of researchers recently. However, limitations such as high cost, complex fabrication and unintended side effects from supraphysiological concentrations of the drugs/growth factors represent major obstacles to any potential clinical application in the near term. In this study we reported an in situ one-pot synthesis strategy of MSNs doped with hypoxia-inducing copper ions and systematically evaluated the nanospheres by in vitro biological assessments. The Cu-containing mesoporous silica nanospheres (Cu-MSNs) had uniform spherical morphology (∼100 nm), ordered mesoporous channels (∼2 nm) and homogeneous Cu distribution. Cu-MSNs demonstrated sustained release of both silicon (Si) and Cu ions and controlled degradability. The Cu-MSNs were phagocytized by immune cells and appeared to modulate a favorable immune environment by initiating proper pro-inflammatory cytokines, inducing osteogenic/angiogenic factors and suppressing osteoclastogenic factors by the immune cells. The immune microenvironment induced by the Cu-MSNs led to robust osteogenic differentiation of bone mesenchymal stem cells (BMSCs) via the activation of Oncostation M (OSM) pathway. These results suggest that the novel Cu-MSNs could be used as an immunomodulatory agent with osteostimulatory capacity for bone regeneration/therapy application. Statement of significance In order to stimulate both osteogenesis and angiogenesis of stem cells for further bone regeneration, a new kind of hypoxia-inducing copper doped mesoporous silica nanospheres (Cu-MSNs) were prepared via one-pot synthesis. Biological assessments under immune environment which better reflect the in vivo response revealed that the nanospheres possessed osteostimulatory capacity and had potential as immunomodulatory agent for bone regeneration/therapy application. The strategy of introducing controllable amount of therapeutic ions instead of loading expensive drugs/growth factors in mesoporous silica nanosphere provides new options for bioactive nanomaterial functionalization.

Analysis of physical activity in emmetropic and myopic university students during semester and holiday periods: A pilot study

Background Previous studies (mostly questionnaire-based in children) suggest that outdoor activity is protective against myopia. There are few studies on young adults investigating both the impact of simply being outdoors versus performing physical activity. The aim was to study the relationship between the refractive error of young adults and their physical activity patterns. Methods Twenty-seven university students, aged 18 to 25 years, wore a pedometer (Omron HJ720ITE) for seven days both during the semester and holiday periods. They simultaneously recorded the type of activity performed, its duration, the number of steps taken (from the pedometer) and their location (indoors/outdoors) in a logbook. Mean spherical refractive error was used to divide participants into three groups (emmetropes: +1.00 to -0.50 D, low myopes: -0.62 to -3.00 D, higher myopes: -3.12 D or greater myopia). Results There were no significant differences between the refractive groups during the semester or holiday periods; the average daily times spent outdoors, the duration of physical activity, the ratio of physical activity performed outdoors to indoors and amount of near work performed were similar. The peak exercise intensity was similar across all groups: approximately 100 steps perminute, a brisk walk. Up to one-third of all physical activity was performed outdoors. There were some significant differences in activities performed during semester and holiday times. For example, lowmyopes spent significantly less time outside (49 ± 47 versus 74 ± 41 minutes, p = 0.005) and performed less physical activity (6,388 ± 1,747 versus 6,779 ± 2,746 steps per day; p = 0.03) during the holidays compared to during semester. Conclusions The fact that all groups had similar low exercise intensity butmany were notmyopic suggests that physical activity levels are not critical. There were differences in the activity patterns of lowmyopes during semester and holiday periods. This study highlights the need for a larger longitudinal-based study with particular emphasis on how discretionary time is spent.

Self-Organization of n-Alkane Chains in Water: Length Dependent Crossover from Helix and Toroid to Molten Globule

We demonstrate a chain length dependent crossover in the structural properties of linear hydrocarbon (n-alkane) chains using detailed atomistic simulations in explicit water. We identify a number of exotic structures of the polymer chain through energy minimization of representative snapshots collected from molecular dynamics trajectory. While the collapsed state is ring-like (circular) for small chains (CnH2n+2; n <= 20) and spherical for very long ones (n = 100), we find the emergence of ordered helical structures at intermediate lengths (n similar to 40). We find different types of disordered helices and toroid-like structures at n = 60. We also report a sharp transition in the stability of the collapsed state as a function of the chain length through relevant free energy calculations. While the collapsed state is only marginally metastable for C20H42, a clear bistable free energy surface emerges only when the chain is about 30 monomers long. For n = 30, the polymer exhibits an intermittent oscillation between the collapsed and the coil structures, characteristic of two stable states separated by a small barrier.

Pressure sensitive flow and constraint factor in amorphous materials below glass transition

The constraint factor, C (given by the hardness-yield strength ratio H/Y in the fully lastic regime of indentation), in metallic glasses, is greater than three, a reflection of the sensitivity of their plastic flow to pressure. Furthermore, C increases with increasing temperature. In this work, we examine if this is true in amorphous polymers as well, through experiments on amorphous poly(methyl methacrylate) (PMMA). Uniaxial compression as well as spherical indentation tests were conducted in the 248-348 K range to construct H/Y versus indentation strain plots at each temperature and obtain the C-values. Results show that C increases with temperature in PMMA as well. Good correlation between the loss factors, measured using a dynamic mechanical analyzer, and C, suggest that the enhanced sensitivity to pressure is possibly due to beta-relaxation. We offer possible mechanistic reasons for the observed trends in amorphous materials in terms of relaxation processes.

Indentation strength of a piezoelectric ceramic: Experiments and simulations

The spherical indentation strength of a lead zirconate titanate (PZT) piezoelectric ceramic was investigated under poled and unpoled conditions and with different electrical boundary conditions (arising through the use of insulating or conducting indenters). Experimental results show that the indentation strength of the poled PZT is higher than that of the unpoled PZT. The strength of a poled PZT under a conducting indenter is higher than that under an insulating indenter. Poling direction (with respect to the direction of indentation loading) did not significantly affect the strength of material. Complementary finite element analysis (FEA) of spherical indentation of an elastic, linearly coupled piezoelectric half-space is conducted for rationalizing the experimental observations. Simulations show marked dependency of the contact stress on the boundary conditions. In particular, contact stress redistribution in the Coupled problem leads to a change in the fracture initiation, from Hertzian cracking in the unpoled material to Subsurface damage initiation in poled PZT. These observations help explain the experimental ranking of strength the PZT in different material conditions or under different boundary conditions.

Miniscleral lens wear influences corneal curvature and optics

Purpose Transient changes in corneal topography associated with soft and conventional or reverse geometry rigid contact lens wear have been well documented; however, only a few studies have examined the influence of scleral contact lens wear upon the cornea. Therefore, in this study, we examined the influence of modern miniscleral contact lenses, which land entirely on the sclera and overlying tissues, upon anterior corneal curvature and optics. Methods Anterior corneal topography and elevation data were acquired using Scheimpflug imaging (Pentacam HR, Oculus) immediately prior to and following 8 hours of miniscleral contact lens wear in 15 young healthy adults (mean age 22 ± 3 years, 8 East Asian, 7 Caucasian) with normal corneae. Corneal diurnal variations were accounted for using data collected on a dedicated measurement day without contact lens wear. Corneal clearance was quantified using an optical coherence tomographer (RS-3000, Nidek) following lens insertion and after 8 hours of lens wear. Results Although corneal clearance was maintained throughout the 8 hour lens wear period, significant corneal flattening (up to 0.08 ± 0.04 mm) was observed, primarily in the superior mid-peripheral cornea, which resulted in a slight increase in against-the-rule corneal astigmatism (mean +0.02/-0.15 x 94 for an 8 mm diameter). Higher order aberration terms of horizontal coma, vertical coma and spherical aberration all underwent significant changes for an 8 mm corneal diameter (p ≤ 0.01), which typically resulted in a decrease in RMS error values (mean change in total higher order RMS -0.035 ± 0.046 µm for an 8 mm diameter). There was no association between the magnitude of change in central or mid-peripheral corneal clearance during lens wear and the observed changes in corneal curvature (p > 0.05). However, Asian participants displayed a significantly greater reduction in corneal clearance (p = 0.04) and greater superior-nasal corneal flattening compared to Caucasians (p = 0.048). Conclusions Miniscleral contact lenses that vault the cornea induce significant changes in anterior corneal surface topography and higher order aberrations following 8 hours of lens wear. The region of greatest corneal flattening was observed in the superior-nasal mid-periphery, more so in Asian participants. Practitioners should be aware that corneal measurements obtained following miniscleral lens removal may mask underlying corneal steepening.

The influence of a novel simulated learning environment upon student clinical subjective refraction performance: A pilot study

Background: Optometry students are taught the process of subjective refraction through lectures and laboratory based practicals before progressing to supervised clinical practice. Simulated learning environments (SLEs) are an emerging technology that are used in a range of health disciplines, however, there is limited evidence regarding the effectiveness of clinical simulators as an educational tool. Methods: Forty optometry students (20 fourth year and 20 fifth year) were assessed twice by a qualified optometrist (two examinations separated by 4-8 weeks) while completing a monocular non-cycloplegic subjective refraction on the same patient with an unknown refractive error simulated using contact lenses. Half of the students were granted access to an online SLE, The Brien Holden Vision Institute (BHVI®) Virtual Refractor, and the remaining students formed a control group. The primary outcome measures at each visit were; accuracy of the clinical refraction compared to a qualified optometrist and relative to the Optometry Council of Australia and New Zealand (OCANZ) subjective refraction examination criteria. Secondary measures of interest included descriptors of student SLE engagement, student self-reported confidence levels and correlations between performance in the simulated and real world clinical environment. Results: Eighty percent of students in the intervention group interacted with the SLE (for an average of 100 minutes); however, there was no correlation between measures of student engagement with the BHVI® Virtual Refractor and speed or accuracy of clinical subjective refractions. Fifth year students were typically more confident and refracted more accurately and quickly than fourth year students. A year group by experimental group interaction (p = 0.03) was observed for accuracy of the spherical component of refraction, and post hoc analysis revealed that less experienced students exhibited greater gains in clinical accuracy following exposure to the SLE intervention. Conclusions: Short-term exposure to a SLE can positively influence clinical subjective refraction outcomes for less experienced optometry students and may be of benefit in increasing the skills of novice refractionists to levels appropriate for commencing supervised clinical interactions.

Preparation and catalytic studies of palladium nanoparticles stabilized by dendritic phosphine ligand-functionalized silica

Silica is a prominently utilized heterogeneous metal catalyst support. Functionalization of the silica with poly(ether imine) based dendritic phosphine ligand was conducted, in order to assess the efficacy of the dendritic phosphine in reactions facilitated by a silica supported metal catalyst. The phosphinated poly(ether imine) (PETIM) dendritic ligand was bound covalently to the functionalized silica. For this purpose, the phosphinated dendritic ligand containing an amine at the focal point was synthesized initially. Complexation of the dendritic phosphine functionalized silica with Pd(COD)Cl-2 yielded Pd(II) complex, which was reduced subsequently to Pd(0), by conditioning with EtOH. The Pd metal nanoparticle thus formed was characterized by physical methods, and the spherical nanoparticles were found to have >85% size distribution between 2 nm and 4 nm. The metal nanoparticle was tested as a hydrogenation catalyst of olefins. The catalyst could be recovered and recycled more than 10 times, without a loss in the catalytic efficiency.

Microemulsion-mediated synthesis of cobalt (pure fcc and hexagonal phases) and cobalt-nickel alloy nanoparticles

By choosing appropriate microemulsion systems, hexagonal cobalt (Co) and cobalt-nickel (1:1) alloy nanoparticles have been obtained with cetyltrimethylammonium bromide as a cationic surfactant at 500 degrees C. This method thus stabilizes the hcp cobalt even at sizes (<10 nm) at which normally fcc cobalt is predicted to be stable. On annealing the hcp cobalt nanoparticles in H-2 at 700 degrees C we could transform them to fcc cobalt nanoparticles. Microscopy studies show the formation of spherical nanoparticles of hexagonal and cubic forms of cobalt and Co-Ni (1:1) alloy nanoparticles with the average size of 4, 8 and 20 nm, respectively. Electrochemical studies show that the catalytic property towards oxygen evolution is dependent on the applied voltage. At low voltage (less than 0.65 V) the Co (hexagonal) nanoparticles are superior to the alloy (Co-Ni) nanoparticles while above this voltage the alloy nanoparticles are more efficient catalysts. The nanoparticles of cobalt (hcp and fcc) and alloy (Co-Ni) nanoparticles show ferromagnetism. The saturation magnetization of Co-Ni nanoparticles is reduced compared to the bulk possibly due to surface oxidation.